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62975
Un 325tn
Engin
cap . 2 NASA TN D  87
D  87
NASA
7
DTN
8
NASA
TECHNICAL NOTE
By Steve P. Heims
SEP 1059
UNIVERSITY OF ILLINOIS
UNIVERSITY OF ILLINOISURBANA
3 0112 106741850
TABLE OF CONTENTS
Page
SUMMARY 1
INTRODUCTION 2
SYMBOLS
I. THE BASIC EQUATIONS AND CONCEPTS
Limitations of Present Analysis
Mathematical Description of the Gas ( Internal Energy and
7
Equation of State ) .
Differential Flow Relations 9
The Local Polytropic Exponent 10
The Entropy in Nonequilibrium Flow ll
Adiabatic Flow 13
The Heat Flow Analogy 14
Explicit Form of the Entropy Function 14
II . ISENTROPIC FLOW . 15
Types of Isentropic Flow . 15
Frozen reaction and frozen vibrations 17
Frozen reaction vibrations in equilibrium 18
Reaction in equilibrium  vibrational temperature constant 22
Reactions and vibrations in equilibrium 25
Application of Foregoing Results Extension of Theory to Air . 29
III . NONEQUILIBRIUM FLOW 32
Relaxing Vibrations 33
Constant density flow 34
Constant pressure flow 35
Isothermal flow 35
Constant cross  section flow 36
Relaxation length 37
Simultaneous Chemical and Vibrational Relaxation Behind a
Normal Shock 38
CONCLUDING REMARKS 42
APPENDIX A 44
APPENDIX B 46
APPENDIX C 48
REFERENCES 49
BIBLIOGRAPHY 51
FIGURES 53
NATIONAL AERONAUTICS AND SPACE ADMINISTRATION
By Steve P. Heims
SUMMARY
Equations are derived from which the one dimensional flow of gases
simultaneously subject to dissociation and vibration can be computed .
The cases considered include both frozen and equilibrium flows and flows
where either dissociation or vibration is frozen while the other is in
equilibrium . These flows are isentropic if no shocks occur in the region
considered and if viscosity and heat conduction are negligible .
INTRODUCTION
the variation of ap
taken along streamlines ; sound speed
dp
el
DT
p
f partition functions
h NOD
enthalpy per unit mass divided by ; also Planck's constant
MAZ
k Boltzmann's constant
M molecular weight
N ,N2 nitrogen
No Avogadro's number
0,02 oxygen
5
p ' pressure
NOD
р pressure divided by m
M
R
S entropy per unit mass , divided by
M A
z
T NOD
temperature divided by
R
t time
u NOD
flow speed divided by
MAZ
NA
X mass fraction of gas dissociated ,
2nA , +1A
d log p
γ derivative along the flow direction of
d logo
1
E vibrational energy per molecule , e ( T ) = 0 exp
o[exp( )1]
λ relaxation distance
р density divided by
μ. constant ( see eq . ( 21 ) )
6
Subscripts
A molecule of type O or N
Az molecule of type Oz or N2
с chemical
D dissociation
e electronic
rot rotational
tr translational
V vibrational
initial value
Superscripts
dimensional variable
time derivative
In the present model of the gas , the small effects arising from
vibration rotation coupling and anharmonic vibrations are not included .
In addition , the simplifying assumption is made that changes in electronic
excitation do not occur . At very high temperatures this last assumption
is not valid because the probability of any particular molecular species
being electronically excited (relative to not being excited ) is approxi
mately given by the Boltzmann factori exp( 0e / T ) , where ee is a tem
perature characteristic of the species . For atomic oxygen and nitrogen
the characteristic temperatures are 22,710 ° K and 27,610 ° K , respectively ,
while for molecular oxygen and nitrogen they are 11,340 ° K and 71,575 ° K ,
respectively . ( In figs . 1 and 2 the fraction of internal energy in
electronic excitations is shown graphically for various species and for
air . )
The nature of the gas is fully specified by the expression for the
internal energy of the gas together with the equation of state . In
mathematical language the model of the gas will consist of these two
equations , which will embody assumption 2 . Since these equations char
acterize the gas , and not any particular flow , they are not restricted
to one dimensional analysis and do not involve assumptions 1 and 3.
To write the expression for the internal energy of the gas , two
additional variables are introduced , the vibrational energy per gram of
gas , ey ', and the degree of dissociation defined by x=na /2nA, +na .
Here X is the mass fraction of A in atomic form .
etr '= ( 3RT' /2MA, )(1 +x) , rotational energy erot '=(RT '/MA, )(1 x) , vibra
tional energy ey ', and energy due to dissociation ep '= (N D /MA ,) x . The
electronic energy is neglected , as is stated in assumption 2 above .
With only this approximation the internal energy per gram of gas is
(
1
)
RT ' 5 + x NOD
el ey ' + etr + x
iterot'tep '  ev ' + MA 2 Maz
Z
5 +x
e = ey + x + TO (3 )
2
and (3 )
21
The word " random " unfortunately suggests that the motion of these
molecules is chaotic , following no fixed laws of motion . What is meant
is that the detailed motion of the individual molecules is not specified ;
nor are these detailed motions relevant for the present calculations ,
since only average statistical quantities are needed , such as the average
energy per molecule . The word " random " is used to distinguish these
individual molecular motions from the collective drift or flow of the gas .
3The quantity h/t is equal to the usually tabulated quantity H /RT ,
where H is the enthalpy per mol of gas .
9
7 + 3x
h = Ev + x + TO (4 )
2
For steady one dimensional flow , in which friction forces and heat
conduction are neglected (assumptions 1 and 3 ) , the conservation equations
derived in books on aerodynamics are
)
5
(
u'du ' + dh ' = 0 ( energy )
dp !
u'du ' = 0 (momentum ) (6 )
alp'u'A ) = 0 (mass ) ( 7)
These first two can be combined to give the implicit condition that no
heat is added to the system :
dp '
O = dh ' = de ' +p'd (8 )
( +)
(
9
)
JDT = 0
u dutdevo(1 + (1+2 )
(10 )
devt(1 + ax + Stufe ar(1+x)? dp = 0
der
dh (7+3x) +(2+31) AT
dx + 2 AT
7 = ( 11)
de dx + dev
(5 +x )+ (2+ T) 2
AT AT
equality 7 =cp/co
y is also true for a chemically inactive gas in vibra
tional equilibrium . It does not hold , however , in a chemically reactive
gas . In nonequilibrium problems , Cp and C are not even uniquely defined .
ll
In one dimensional flow , however , the speed , Vy( p /e) , does have in
any case one special significance ; namely , it is a direct consequence of
basic equations (6 ) and ( 7 ) that at a throat of a nozzle, unless dp ' = 0 ,
the flow velocity is related to > by
Uthroat (p /p ) ( 12 )
e
€ ( Tv ) Iv_ (13a )
1
e o /
or by its inverse :
12
o
(135 )
Ty  loe(  ) 2** ]
.00[1+0(
HICU
ds + (1x)\T(1 e6 /Tv) + dx
dev
Tv + x 5 T  (1+x) * +106
px2
터
( 14 )
(1x),/T(1e e /T) =
HIE
log
px2
and the right  hand side of equation ( 14 ) reduces to the left hand side
of equation ( 10 ) divided by T. For this to be true , it is necessary to
use a unit of density which depends on the gas p =pi/ c , as is discussed
in appendix A. This constant density C for different gases is listed
in appendix B.
Adiabatic Flow
For adiabatic flow the expression for the entropy change is obtained
by combining the condition ( 10 ) , no heat exchange with the surroundings ,
with the general expression for the entropy , equation ( 14 ) . The resulting
entropy change will then be entirely due to the irreversible relaxation
processes :
( 1x ) + (1 e e /Tv )
HIE
(15 )
asdevlet
va )tax[106 px ?
дх dev
( 16 )
ƏXV axd eq
eq
The subscript eq means that the derivatives are taken at the equilibrium
value . This relation may become useful when one, for example , has
knowledge of vibrational relaxation rates for gases not in complete
chemical equilibrium , for then equation ( 16 ) gives information about the
reaction rate in flows where the vibrations are out of equilibrium . Were
14
it not for the high activation energy of the dissociation reaction , the
equation ( 16 ) could be replaced by a linear algebraic relation between
the forces and the fluxes .
1
dS = de ( 17)
T
II
This quantity is always positive because the heat flow is always from
higher to lower temperature .
Хо
now
1  X0 1 X oo
S So = + log (1 e e / Tvo ).STO X + +
SoL px 1 xo x Tyd
+ 5 +x log ( 18)
(1x ) log  (1+x)log 2
with o = eyte ( 1  x ) and Oo= evo +0 ( 1 x ) . The first four terms of equa
tion ( 18) arise from the change in X and from the variation in vibra
tional energy , and the last two terms arise because of the density and
temperature change . The expression (18 ) thus gives the entropy in a
vibrating reacting gas regardless of whether it is in equilibrium or not .
The familiar expression for entropy , when no vibrations and no reaction
is occurring , is obtained from equation ( 18 ) when ey = evo and X = XO :
A more compact way of writing equation ( 18 ) is
1  Xo
( 1  e e /Tvo).JT. (x xo )+ +
+
+ log
SSo = 3 , P.X. Fo ](xxo)+( Tvo
5 + X
2x 1 X 1 +x 2
Хо 1 X T
log
1  XO TO
II . ISENTROPIC FLOW
(192 )
deve.  £)tax[108 byt 1+(129/Tv)  10
ey= ( 1  x )
16
(19 )
dev = 0
and
dev ( 1 x )de  € dx = 0
1 E
px ?
UNT e T = K ' ( T , Tv ) (21 )
1 x
5 +x 7 + 3x
y =
Cy = 5 2 Cp = 7+3* 5 +x
dp
54x 4T = (1+x)
giving
2 + 2Xo
5 + X0
( 222 )
For a pure diatomic gas, the exponent is 2/5 and for a pure monatomic gas
it is 2/3 . Using equations ( 2 ) and ( 9 ) , one readily has the further
relationships
7 + 3X0 7 + 3x0
2 + 2X0 5 + XO
alai
ele
= ( 226 )
5 +Xo
2 + 2X
A To uo
(220 )
A. . T
A Vuo2+( T.T) (7+ 3x )
For any given channel shape A ( y ) , equations (22) give the temperature ,
pressure , velocity , and density distribution . The entropy is from
equation ( 14 ) given by
5 +x (22e )
S =  ( 1 +x ) log p + 2 log T + constant
ev = ( 1  x ) € (23)
with
A Ꮎ
€ (T) T (23a )
2
e e / T1 e / T<< 1
The number =ov /0D is a constant characteristic of the gas and is equal
to hv/ D , where hy is the energy of a vibrational quantum of the gas ,
and D is the dissociation energy . Inserting equation (23) into
equation ( 14 ) readily verifies that the entropy is a unique function of
T and p . Integration of equation ( 14 ) and of equation ( 9 ) after the
expression (23 ) is inserted for ev , gives with the help of the equation
of state ( 2 ) the following relationships :
7 + 3x0
2 + 2Xo
HA
T
p exp ( 1  Xo J
II
( 242 )
Po 1 +x0
5 + Xo
2 + 2xo
p 1xo
exp J (246 )
1 +xo
5 + Xo
2 + 2Xo
A exp 1 xo J Uo
A. 1 + x0 uo2+( T.  T ) ( 7 + 3x ) +2 (evo  ev )
( 240 )
where J is defined by
20
e e / To 1 1 e 1
+
21
J =
LO /To zeżaz  108
JO / T e / T_
1 l  e 0 / T l  e o / T
( 25 )
de 5 +X0 de
CV + ( 1  x ) ат ( 26a )
2
CP
dh 7 + 3x0 de
+ ( 1 xo) ( 266 )
от 2 dT
p
de
7 + 3x + 2 ( l  Xo )
AT
y = ( 260)
de
5 +20+2(1xo ) dT
Cp Cy = ( 1 +x ) ( 260 )
as is evident from equations ( 26a ) and ( 26b ) . The expression for de /aT
required in equations (26a ) , ( 26b ) , and ( 260 ) is obtained from equa
tion (23 ) :
2
de € 0/T 1 (27)
AT
e / Tx < 1
21
5 +x +
S =  (1 +xo ) log p + (28 )
2 log TH(1x0)(€¥€+ 206 €)+const
When
Compa
Өо
>> 1 and >> 1 (29)
7  Xo 9 + x0 9 + X0
Cv 7 (31 )
2 Cp 2
7  xo
9 + XO 9 + XO
2 + 2X0 7  Xo
р
( 32a)
u24.2= ( T.  T ) (9 +x ) ( 326 )
22
7 Xo
2 + 2Xo
A To Uo
( 320 )
Ao
u.2 ( 9 + xo ) ( T  T . )
1 E
px2 T
K ( T , Tv ) = = u
u nte
1 X (21 )
with
ure €/Tv(1e/Tv)
(16 )
T
1 X
p
HNT e
Il
( 33)
x2
O = as = [2 ( 1  e ) + ( 1 +x ) (x  2 )]
( 34 )
2T (1
.** }{1e)Jar
x ()
** 1(
x
x ) 2)]ax+
( 1 + x ) (1€ ) + 3 Tx
S = + integration
T
x + 2 log constant ( 35 )
လ
ယ
( 1  x ) (1€ )
Finally , one obtains the cross  sectional area from equations ( 33 ) and
( 36 ) , and the continuity equation :
24
1 E
Pou exp T
A. x2
A. 1 X
] T [ 2 (16 ) (xo x )+7( T.  T )+3( Toxo  Tx ) + u62 ]
HIA
x2 Pouo
[ 2 (16 ) (xo x ) +7 ( T.  T )+3 ( Toxo  Tx ) +u62 ]
1 x K ( T , Tv )
(37)
dx
( 7 + 3x ) + (2 +3T 28 )
AT
7 = ( 38 )
dx
(5+x)+(2+T2e) AT
+

5 +x дх
( 39a )
2 DT
dh
(39 )
II
ср
от, 743x +(1 + ŹTe)SA
* (1 x ) 1 1 €
2 (40a )
от, 2  X 2T T
K(T) – Do  VT (1eC/T)e /T ( 20 )
>> 1
H10
(41)
<< 1 ( 42 )
LA
in which l e /T_e /T . The general expression for the density is in view
of equation (20 ) :
26
p = 1X
 T ( 12 /T)e 1/T (43)
x2
/1
p = 0 l x e 1
(44 )
x2 T
P = const l  x e  1 / T (45 )
x
Lighthill shows that for oxygen and nitrogen his " constant" is really a
slowly varying function of temperature which is increasing for small T
and decreasing for large T , and has a maximum in the neighborhood of the
0
..
VIE
(46a )
1 +x Tx +
S.( 0 ) x + 2 log + + 2 log
T 1 X (2° /Tx )
(47a )
So = 4x + (476 )
+ 2 log Mex
27
T * 1 +x
4 (48 )
5To compare with the tables of Treanor and Logan , it should be noted
that they tabulate ( S /R ) which for oxygen ( ref . 19 ) is so (0 ) + 24.30 and
for nitrogen ( ref . 20 ) is Sole ) + 24.07 .
28
A 2 Pouo
A.
A 1 x
K ( T ) / uo2 + 2 ( xo  x ) +7 ( To  T ) +3 ( Toxo Tx ) +2 (evo ev )
( 50a )
e1 / T NT Pouo
A x2 o
(50b )
Ао 1 X
u2+2 (x , x ) +9 ( T.  T )+ (Toxo Tx )
dx
9 +x + (2 + T)
7+3x+2(1 x) de + (2 +3Te ) dx AT
y =
Ole
de dx + dx
5 +x +2 (1 x ) + (2 + T  e ) « 1 7  x + (2  T ) AT
AT ат
(51)
1
1
+
(146b )
am LixPix) T(1+x) 2 (1 +x ).
+
(52a )
Cop  ) 5*++* . ) + 1x) die
29
dh 7 + 3x + de
ср ( 52b )
DT 2 AT
(1 + 1  ) ) +1+x
)
* (1 x ) ( 1
(53a )
2 X 12 2T
+
(53 )
(1x2)
**K/20 ( VI+Hp/  )
no
0 (54 )
# 2 2no th
a o
(55a )
ev=0.77€ ,+0.23(1xo,) ,
ev = e (10.23x02 ) (55b )
T (0.23x0,) + 2 log e
(56 )
oxygen ) , and the correct value for Maz is 29.0 ( the mean molecular
weight of cold air ) .
Calculation for air in the range where the oxygen is almost completely
dissociated and the nitrogen is chemically active can also be carried
through . At first sight it would seem that at these high temperatures
one would have to include the electronic energies . Actually it is not
much of an error to neglect the electronic energies provided most of the
nitrogen is undissociated ; when most of the nitrogen is dissociated the
error becomes important . The reason for this is that molecular nitrogen
remains in its ground state until extremely high temperatures , while
atomic nitrogen is more readily excited . In figure l are shown the percent
of energy in electronic form of each of the four species , 0 , 02 , N2 , and N ,
as a function of temperature . Figure 2 gives the corresponding result
for air . For example , at atmospheric density at 7000 ° K , the fraction
of the energy in electronic form is , according to figure 2 , about 1/2
percent , certainly not a prohibitive amount for approximate calculations.
At the high temperatures where electronic excitations contribute at
equilibrium , application of the present method would give the frozen
excitation limit for the flow . When nitrogen is dissociating and the
oxygen is in completely atomic form , we require
NN
XN2  2nNa (57 )

(58 )
p = ( 1.23+0.77% 92 ) FT
HICU
erev + (5.23+0.77XN_ ) + 0.77% N2 (59)
I
N2 (60 )
( 7.69+ 2.31XN2) + 0.77X
The vibrational energy is due only to the nitrogen vibration and so its
equilibrium value is of nearly the same form as the vibrational energy
+
T
0 (1 XN )
now
2
along the tube . The tube will of necessity have constant cross section .
In relaxing flow constant pressure , constant density , and constant cross
section are generally incompatible . We can ask , however , " Given a constant
cross section , what will the pressure and density variation be ?" or
" Given constant pressure, what will be the shape of the streamtube ?"
(See fig . 5 , to be discussed later . ) A more general form of the required
constraint would be knowledge of a channel shape A ( y ) or of a pressure
distribution p (y ) . In references 7 , 8 , and 10 examples of relaxation
with specific channel shapes are worked out in detail .
Relaxing Vibrations
(61 )
d log A = dp + du
d log A dev
II
dev
17
d log A
=
Pult
d log A dev
(temperature constant ) (620 )
II
dy To u2 ) dy
34
p (y ) P2
T( y) p ( y) 2 evly )
= 1
T
2
T2 P2
35
1/2
Aly ) Uz evly )
1 + 4
Az u (y) [1 uz²
T2
s(y) = Sy+plev )  108 T
where
p ' = Pa'
u2
T (y ) A (y) P2 evly )
1
T2 Az ply ) og erT2
ty
log
S S2 = olev)  1 T
Isothermal flow.
T (y) T2
2ev ( y )
u(y) 1
Աշ
Uz²
DET
= exp evly )
T2
explovyky? ]
36
Az 2ev ( y ) evly )
exp
A ( y) u22 T2
S S2 olev)
For isothermal flow , the vibrations may never be able to reach equilibrium ,
because only the kinetic energy (1/2 ) u , 2 is available for conversion to
vibrational energy .
A (y ) Az
elle
u =
Uz
2
T 2 U₂ 1 P2
T2 p T 2 р
[1 +
= 1 +
P2 1+ 0 )
(
122
7
ev ( T2  T ) + Uz2
log 1 +
SSę = pley)  108  log
(12
AT
T
dp
37
Integration leads to the above formula . This is the only one of the
above formulas for which the derivation is not fairly obvious .
not of the polytrope form p /pe= ( /p>)" . For the corresponding result
which includes finite reaction rates see equation (67) .
evly) = eve [1
exp( :) ]
= 0[1exp(5 )
where eve is the equilibrium vibrational energy , which for strong shocks
is approximately equal to the local temperature . Then the simple resulting
behavior is ( see sketch (a )) :
eylo
T A
Ž (5+2ey /a, (63)
T2 A2
Large à
Intermediate a
Small
Pe
A T
Az T2
Sketch (a )
38
It is seen from equation (63) that the area changes by a total of 2/7 of
its original size , and that this occurs over a very short distance if a
is short , and over a long distance if is long . For the large a
limit the flow is frozen and the cross section constant as the sketch
indicates . The small à limit is equilibrium flow , and constant cross
sectional area , constant temperature , and density . Were one to sketch
A/A, as a function of y /1 , the three curves would coincide , indicating
that a is an appropriate unit of length , from the point of view of
similarity .
The flow behind a normal shock wave where vibrational lag and
dissociation of the gas are occurring simultaneously is next discussed .
Freeman (ref . 6 ) has discussed the case without vibrational relaxation .
We shall consider the case of constant cross sectional area , so that the
results apply to the interpretation of shock  tube experiments .
pu= m (64 )
dp du

= 1 ; u (65 )
du dh
39
ela
1 + x
T (66 )
m
The relation between pressure and density is seen from equations (65)
and (64 ) to be not of the polytrope form , but
m m
P  P2 (67)
(1 +x ) (uz+ P2  p ) (68 )
Use of expression ( 4 ) for the enthalpy gives for the vibrational energy ,
2
1 +x
ev = h2 + (69 )
2 I (7+ 3x )x
na + { uze)
In solving flow problems one may have the inverse situation from
the experimental one just described . One may have a good idea of the
relaxation times of the vibrations and the reaction , that is , one knows
x ( y ) and evly ) , but would like to calculate the effect of these rate
processes on velocity , pressure , density , and temperature . Thus , x and
еу are regarded as the independent variables and the velocity , etc. , is
is expressed in terms of x and ev : Again , everything is known in the
40
2
12
+ hz h (70 )
2
Ma 2 ha)1
7 + 3x
(71 )
(uzeth2) ev x ]u(uzu+ P2 )
2 (1 +x )
u (x , y ) P2 B  VB22018
( 72 )
Uz alla
p ( x , ev )
with
7 + 3x
B = ( uz + pa)
2 (1+x )
2 (3 +x )
a =
1 + x
2
Uz
8 +
+ h2 ) ( ev + x )
2
although , in fact , there are no diatomic molecules in that region and the
vibrational energy should be zero .
ev 18 € ( Tv )
ev (73)
s
1 x3 € (T3)
ev
ev3 1 X (1 e y /nv ) ( 74 )
1 X3
X3
fv ( Tv )
l exp ( y /1v e / T2 )
It can be seen from equation (75 ) that even when y /1c >> the
dissociation keeps changing as long as vibrations have not reached their
equilibrium . This is physically correct because the temperature keeps
42
CONCLUDING REMARKS
e / Ty
Sy = ( 1 x ) log (1e 0 /Ivy (A1 )
Ival
e o
x +5
Str + rot log T 2x log 2px ( 1 x ) log ( 1  x ) p +xs + (A2 )
2
( 1 x ) 5 +x
ev T (A3)
Iva etr + rot 2
o l
e
ev o / Tv)
Sv . ( 1  x ) log ( 1  e
Tv
dev
asy log(1e 6 /Tv)ax (A4 )
TV
45
di
ha
x + 5 DT dp ( 1 x ) T
dStr + rot + log l +st Jax (A5 )
2 T (1+x)
4p'x2
tlax
dev
ds +
*  (1+x) et +( 20g (1x) T (120/Tv) + const ldx
TV p'x2
(A6 )
The const can be evaluated from the entropy constant st. Alternatively
it may be evaluated from the equilibrium constant as follows :
(1x) VT (126/T)
HIE
pix2
Furthermore , the equation for the equilibrium constant is (again , see any
book on statistical mechanics ) :
APPENDIX B
MAZ'
е e C,
Gas love °K
a OR , LOD , K A
8m /mol gm / cm3
هیم
H2 2 6324 84.971 51,9501 1 2.130
(
11,300
st
228 327
02 + e T ! T '
32 2274 2.059 58,960 8.8 ( 5 + 3 e T ' 3.3  3 + 2 e 1317
T '
Br2 160 465.1 .1156 22,8804 4 +2 e 1 1761
10,910 17,107
254 308.8 T ! 1 1 +6 e T ' 2285
I2 .05340 17,8954 4 +2 e (176
Note :
hv h2 D Ov
1 . Symbols : Ov =
k өR OD
812IK өр
4. The quantity
3/2
( Tek ) (FAO )2 5/2
C =
8D2/20R
21 e MA
hv. 572 20 FAZ
8
CORAZ
( fa ) ?
 1.10x10401 M 5/2 gm
D e A 3
cm
48
APPENDIX C
x2 na ?
K (T ) =0 = const
1 X DA
Z
2
na (73/2 , e  1 / T
A = const = const VT (126 /T)e 2/ T
II
TAZ f
Az
(15/2)(1e8/7,
In the numerator the 73/2 comes from the three translational degrees
of freedom of each atom . In the denominator the 15/2 is from the five
degrees of freedom of a dumbbell diatomic molecule three degrees of
translation and two of rotation . ( The spinning about its own axis is not
Finally , the e 1 / T factor simply takes into account the fact that
between the ground state of a diatomic molecule and the ground state of
the dissociated atoms there is a certain dissociation energy D. If
T
REFERENCES
14. Chu , Boa Teh : Wave Propagation in a Reacting Mixture . Heat Transfer
and Fluid Mech . Inst . Preprints of Papers , Stanford Univ . Press ,
1958 .
AERODYNAMICS
Introductory
Advanced
Mayer , Joseph E., and Mayer , Maria G .: Statistical Mechanics. John Wiley
& Sons , Inc., 1940. (Emphasizes applications . )
IRREVERSIBLE PROCESSES
Books
16 เ Els
dissociation ,
I
x
2 O
= 9.5 k° ee
2
of
12
energy
1.
*
minus
X IO 3
e
8
atom
n /a
per
4
energy
0
3 4 7 8 9 IO
Internal
O)
2
1
x
K
,03
Temperat ure
a
O)a( tom
temperature
of
f unction
energy
as
internal
average
Distribution
Figure
a1.
53
20
54
Op
ee
16
dissociation ,
Өр
K°31x5
=06.6
2
of
energy
21
to
10 ° 3
x
minus
x
e
8
atom
mlov
per
4
energy
O
2 4 6 7 8. 9 10
Internal
3
g
1
x
%
,0
Tempe rature
a
N)(b tom
.
Continued
1.
Figure
50
OK
40
103
x e
x
е
e
.е
30
ev
molecule ,
20
per
energy
10
whes
Internal
10
O
2 3 4 5 6 8
7
9
1
x
K
°
,03
Tempe rature
molec
O
)c( z ule
1.
Continued
.Figure
55
50
56
negligible
:Electronic
Note
energy
scale
this
on
OK
40
x
& Ol X
30
ev
molecule ,
20
per
energy
10
no/or
Internal
O
2 3 4 6 7 8 9 10
ܗ
103
x
K
°
,
Temperatu re
mol
N
)
d
( a ecule
Con ureded
.1.clu
Fig
10
8
S
PL sea
level
Atmospheric
at
density
air
for
%
3
6
energy
energy
Р
1
= 02
PSL
.
4
internal
Electronic
Total
2
P=1.
0
PSL
O
4 5 8 9 10
3
6
7
2
1
x
K
, 03perature
Tem
electronic
.
air
for
excitations
percent
of
form
the
in
energy
internal
of
The
2.
Figure
57
58
.8
of
units
BR A n
Entropyi
Mi
log
S=(1x?6
+*+ 2 Tx
)1x(16
5=3
SMAZ
5:15
$+20
.08
.06
.04
:T
992
K
5000
.08
.06
.04
25
20
.01
.001 .002 .004 006 .008 OI .02 .04 .06 .08 .2 .6 .81.0
4
dissociat
of
,dx egree ion
equilibrium
in(b)Ofull
xygen
Figure
Continued
.3.
59
60
.8
.6
Aą
quation
70
4eM)(,ŘSo
.2
SA
10
&
10,000
.08
.06
PRO
5,000
.04
dissociation
dof
x, egree
full
equilibrium
Nin(C) itrogen
3.
Concluded
.Figure
1.0
Exact
Approximate
o
.8

.6
& 01 = 0
2
dissociation , x
p = 10
of
4
1
p = 10
Degree
.2
1=.0
p
=p10
1
K
°
,
Tempe
x 03 rature
)
(
disso
f
a
as
tempe
of
.
Equili
uncti
ciati
ratur
brium
on one
by
those
obtai
with
for
oxyge
quant
tabul
exact
of
Compa
4.
Figur ned
n
ities
ated
the rison
e
mathematical
paper
present
in
used
gas
the
of
.model
19
20
62
Exact
Approximate
O
3
16
p = 10
†
2
P = 10
12
1
enthalpy,
p = 10
8
1P=.0
1p=0
Dimensionless
o
2.0 2.4 2.8 3.2 3.6 4.0 4.4 4.8 5.2
1
x
K
°
, 03 rature
Tempe
.
tempe
of
a
f
as
E ratur
uncti
entha
)quili
b
( on
lpy
brium e
Concluded
.4.
Figure
A.
Consta
area nt
B.
Constan
pressuret
3 Constan
C.
;M,~6density t
Constan
density
,~1;MD.
2 t
section
Constan
tempera
M,~1;E.
2 tture
Consta
tempera
;M,~6F. nt
ture
wave .
initial cross
2
to
shock
section
behind
immediately
of streamtube cross
Ratio
O .01 . 1.0
z= ey
Tz
shock
,f
n or
ormal
behind
streamtubes
shape
aof
on
relaxation
vibrational
Effect
of
Figure
5.
.
constrain
differing ts
63
얻
1.2
.
Equilibrium
1.0
ev
eV3
.8
4
13
Xz
.68
_.64
.6
11
4
.2

.4 4.0
3.6
3.2
2.8
1.2
1.6
2.0
2.4
λα λο
.8
oflv
units
in
behind
d istance
y,shock
3
d=
)
ac1v
(
dissociat
and
vibration
molecular
the
of
equilibri
to
approach
simultane
The ion
s
um
ous
6.
Figure
.shock
anormal
behind
1.2
Equilibrium
1.0
ev
ath
.ev
.8 .78
.64
.6
.2
AX
O .8 1.2 1.6 2.0 2.4 2.8 3.2 3.6 4.0
lv
of
units
in
shock
d
behind
,
y istance
17
.
d c
)b( 5
.
Concl
6.
Figur uded
e
65
1.7
66
Equilibrium
%
100
95
%
1.6 0=Ac =.5
Ac
%
80
1.5
1.4
(0 )
ply )
3=
Lhc
1.3
Density
when
Equilibrium
%
32 frozen
reaction
enz
1.2
 +
dc
Eco
%15
1.1
1
%0
1.0
3.6
2.8
2.4
4.0
O 1.2
lv
.841.6 2.0
3.2
shock
lv
of
units
in
y,distance
behind
A  153