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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 ILLINOIS-URBANA
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 + (1-x)\T(1 -e-6 /Tv) + dx
dev
Tv + x 5 T - (1+x) * +106
px2
터
( 14 )
(1-x),/T(1-e -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 :
( 1-x ) + (1 -e -e /Tv )
HIE
(15 )
as-devlet
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 + +
So-L px 1 -xo x Tyd
+ 5 +x log ( 18)
(1-x ) 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
S-So = 3 , P.X. Fo ](x-xo)+( 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+(1-2-9/Tv) - 1-0
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 / T-1 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 1-xo
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(1-xo ) 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(1-x0)(€¥€+ 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)
u2-4.2= ( 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(1-e--/Tv)
(1-6 )
T
1 -X
p
HNT e
Il
( 33)
x2
O = as = [2 ( 1 - e ) + ( 1 +x ) (x - 2 )]
( 34 )
2T -(1
.** }{1-e)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 (1-6 ) (xo -x )+7( T. - T )+3( Toxo - Tx ) + u62 ]
HIA
x2 Pouo
[ 2 (1-6 ) (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+T-2e) AT
+
-
5 +x дх
( 39a )
2 DT
dh
(39 )
II
ср
от, 743x +(1 + ŹT-e)SA
* (1 -x ) 1 1- €
2 (40a )
от, 2 - X 2T T
K(T) – Do - VT (1-e-C/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 ( 1-2 /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° /T-x )
(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 +3T-e ) 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*++* . ) + 1-x) die
29
dh 7 + 3x + de
ср ( 52b )
DT 2 AT
(1 + 1 - ) ) +1+x
)
* (1 -x ) ( 1
(53a )
2 -X 12 2T
+
(53 )
(1-x2)
**K/20 ( VI+Hp/ - )
no
0 (54 )
# 2 2no th
a o
(55a )
ev=0.77€ ,+0.23(1-xo,) ,
ev = e (1-0.23x02 ) (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 +
S-Sę = 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[1-exp(-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+2e-y /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(uz-u+ P2 )
2 (1 +x )|
u (x , y ) P2 B - VB2-2018
( 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 1-8 € ( 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 (1-e -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(1-e -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 (1-x) T (1-2-0/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 :
(1-x) VT (1-2-6/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 ) ?
- 1.10x10-401 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 (1-2-6 /T)e -2/ T
II
TAZ f
Az
(15/2)(1-e-8/7,--
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
,0-3
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
10-3
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
°
,0-3
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
10-3
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
= 0-2
PSL
.
4
internal
Electronic
Total
2
P=1.
0
PSL
O
4 5 8 9 10
3
6
7
2
1
x
K
, 0-3perature
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
)1-x(1-6
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 0-3 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
°
, 0-3 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