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 , 6.1
(WI)
€W.

* RTD (WLR) TM-63-Z

A SUBROUTINE FOR TIE EQUATION OF STATE OF AIR

RM~RN TO
COPY;(WUL-2)
LOANAFWL.
by KIRTLAMI AM N M EX

L. R. Doan G. H. Nickel

I/Lt USAF /Lt USAF

May 1963

.I TECHNICAL MEMORANDUM NUMBER RTD (WLR) TM-63-Z

Research and Technology Division

Air Force Systems Command
AIR FORCE WEAPONS LABORATORY
KL-fLwd AJr Force Bage
New Mexico
BEST AVAILABLE COPy

Project No. 781I, Task No. 781102

- -- -:. - . .
$ -m ...-...--

! ,. I.

I' ! HEADQUARTERS
AIR FORCE SPECIAL WEAPONS CENTER,
Air Force Systems Command
Kirtland Air Force Base
New Mexico

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Copies of th l.ction.
Address all re q hs domment Is subji t to -sjoeal, 'B. N Mex.
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gowianits Or foreign natioqals my be :~

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Zabw*to~s KviwlM 4FI,
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"-o- Mex. VU7.. -

 RTD (WLR) TMt-63-Z

ABSTRACT

A "semi-y.hysical fit' to the equation of state of air in generated from

( tabulated values. The form to

P ly -l) Pe

Y y (P. 8)
pMass/volume
c energy/mass

A listing of the FORTRAN wabroutine AIR to given, as well as a graph

*of tabulated sad sabroutne-computed values of ly - 1).

Chief, Phystka I~razkh

RTD (AWLR) ITA-63-2

i. A SUBROUINE FOR 2THZ AEUATION OF STATE OF AIRf

Computer calculations of expanding iirebafl in the atmosphere require

some form of equation of state for air which is valid over many orders of
magnitude variation in density and energy. Many SHELL calculations have
been ma~de using an equation of state which appears much toc simple. Nlow-
ever, th.'se calculations havf? given results for fireball growth and rise
which agree amazingly well with experiments. Unfortunately, these results
cannot be expected to give reliable pictures of temperature within the fire-
ball simply because of the Inadequacies In the equation of state. The
distrihution of temperatures wit)'in the fireball Is extremnely important in
fireball calculations since it deterinues electron diesity. This note
describes an interim effort to provide a good equation of state for computer
codes.

Previous, STMELL calculations have used if e < eion, orY

if e > o where e ion Is an input value. The two values: of y were
chosen before each problem by referring to~the real equations of state. We
decided to try a simple fit to (Y-1) for an ideal San eqIaton of state. as
computed by imS. 1 The variables which define this equation of state are
chosen as material density and .uiergy density (per masty) rather than
density and temperature. Hydrodyniamics calculations uilways involve
matertal and energy densitica,, and temperature is niot uszed &s an inde-.
pendent variable.*

The first look r possible forifor this fit weai directed td thic daiuiity
dependence. Cresspts of (yt-) veir6us density foir dfeetegr
vealed, an approximate bohAvior of th. form-

*Tbiz fact rules oat the use of anytft oteemtno saeo ir

using ftemprataxit as an tnd" i a be varlabin -~Ii1~0E~a~by---
RTD (WLRI rM-63-2

-Q sea level density

3
= 1. 293 zl10 3 gm/cm

The exponent a determines density spreading, and is zero below z I

jerk per megagram or 10~ ergs per gram. Above e 1 a (e) is
roughly linear in top, (e) (see figure 1). Assuming the density dependence
discovered, the problem reduces to finding a fit for T (P 0. r). The energy
dependence of (y-1) is Influenced by the dlisor-ition of the major con-
stituent molecules (ozily oxygen and nitrogen contrIbute much to the
thermodynamic properties). There are four different "regimes" which
are defined balow

1. Nothing disociated< e < -

H. Only oxygen dissociated -9 < e< -30

111. Everythinigdissociated 50(<6a< - 150 1

IV. Electrons contributivg ISO15 < a <'

Each "regime" has Usi own energy dependence, and the thermodynavric
properties of air are those of whichever Siregimell represents the composition
of the air. Transitiopis iu properties are made as the composition chMnges.

Regimes I and UI are affected primaarily by the increasing occupation-of

vibratiopal and electromic levels oL.-,pftdi.clfted maecules. The eneirgy
depenz A eiin ~
~ su oi~e~gocp~9zQ
levels. and regime IV to. the thresh*of.the Fexnd-Tboaft dosc'iptiqu,.
Thaw yaicallY. (T-1) is the same an Zju, where a is the uaunbeRp
af degrees .f freedomo. In *,gas whose molecules or atoms have internal
RTD (WLR) TM-63-1

.V4

(a

444 1 4

-- w'z
RTD (WLR) TM-63-Z

structure, n need not be an integer.

For example, an oxygen or nitrogen
molecule is rotating but not vibrating at room temperature, and has an n of
3 + 2 = 5. An energy increase will make n change from 5 to 7 (although
the molecule may dissociate before n reaches 7). Regimes I and HI repre-
sent this change . plus electronic excitation, for 0 and N 2 .

The hump of Increasing at e = 8 is due to the decrease in n for

y
oxygen from 7 to 3 as the molecules dissociate and can no longer rotate or
vibrate. A similar increase in y andoccurs as the nitrogen dissociates,
again as the electrons* (with no nternal energy levels) become numerous.

A fit to y (p 0 , e) for the entire iaterval could be generated by a large

polynomial, but there is more physical significance in a series of experi-
mental fits for each regime which are "turned on and off" as the composition
changes.

In practice, "on and off switches" of the form

fI
+ expX C1

have been found to cause suitable transitions at the "humps " between
functions which have been chosen to fit the data closely between "Lnumps."
These switches have-values from 0 to I ith a certainwidth (-6&e)
centered about the energy r° and have no particular physical significance
in this work. It seems reasonable to however, that --e i re-
lated in some way to the dal. sad Ae -to the -is op
.. . . ,
. .. .. .. . . . . .. . .. . . , - -' +. - %

equilibrium constant. - -

- 1 -r " * . -

*An exciMdatam has mn avlable ena gy states in vIch elc

may res -t a42I1amzwp u- w rc -ha

anj the' uard_++esu t a a t+ • " . _ -,,L- .gr

.+ -sat+ua
....~ . 5t3~haderau&Vt~
£.e ~
h. atm.
.+ !'ih .. ~gre6
RTD (WLA) TM-63-2

If w-- cboooe to fit the d~xta with exponeimtials of the forra.

Ae i

then our method leads us to the foIlow',ng form for the equ~ation of state:

p0

a(C) af
a + a 2 (-~ (iY + 0:3 (Y~

(We might expect the density opread to be different for-each regime.)

1 1 40gz
r-' a- P2109~
St G P3 .

The "swijlbhSl ar kim by -

tO2WU
-fL

- 2.

411
 (Electrons) 3=I

i This is still not complicated enough to give a close description, since each
transition energy and width decreases with decreasing density. This density
dependence was represented by

e =ZOZa etc. amd

Oc
0 .,- 2 0 = : e..'.P
The co stants were evaltuated by a very straightforward technique.
guess Values, Plot curves. guess nw values. Twnard the end, the curves
were comlputed by nzacbluae, but the same td.chique was followed. After
man~y tedious attemnts. each £4KUiug a little closer, it was decided to stop,
call this an interim equation of state, and constinue with more dignified
tecbziiques. rhe resrits of the program to date indicate that the apprakch
is worthwhile. Rsther than list values for each consant (which will prob-
ably change later) we list a subroutine Jappendx 1) in FORTRAN whtchl wl
produce (y-1) with an error generally iron 0-a percent with occasional
Increases to 5 percent. Time tabulated and fitted-vases of 1l'-l) a Slyve
in figure 2. The equations with nubers app.ir in apendix H. Tempera-
tures Mbuve 1. 5 ev were not Sg"enmch o.sdra sinc e radiation Uraus-
pors influemces things above that tprtran& our plinned appliaton
is for !,Sile 9"hobyamitcs amy. It may be jpossihe to centinue the
-descripion ot regime a Tolfmt
- Frter.~liAtionsd this ait ay~e r~s~~~ aqwtiaa of.
I state, - VM fl*Uc-.4d
avowlo rsIyb~
-idi The earn fs~ myude eg~ and *MiVP

Jt

- ~ -U
 AtA

-J

Figure 2. ZqStieO .t wtfta 09 Oair

7
 RTD MR,"i TM-63-2

Lt. J. D. Garcia has suggested that altering the energies of transition may
account for uonequilibriu& efflects In dissociation as the fireball expands
rapidly. This seems qaite possible, once it can be determined how to
0 compute the new transtton energy. Techniques to determbto the coefficients
from theoretical methods (as opposed to curve-fitting) may vicover new
freadom in generating equationk of state for other gases.
Flinally, the continuatio~n of this work to include equations of state for
earth, fire, and water will allow calculations for all possible substances.

I4

3-, '
 RTD EWIJR) 7h(-63-2

Appenadix I

$ A ISTING OF THE FORTRAN*SMROUTIM AIR

wi -
 ~VIT TO 121 ! UftU0 414io 1

* QJW~.1 1~4C, VO 1 A0
~tis1 AA fsU ztl% t
tTERt5
4A~~ DfRAITY

SjfAXAME Stan$ * t iii im;,j * p*MaEjj

znx zwm IIkV OW,
MAW Positive IF NEGATtvto Ar4 cOmY9)T To U 03
T~EFI~Ta At 10HWW OlYC3.R AweS Wh1RON DISSOCIATE 13 A
1r:,CW
Cr VftTT

EAC TRAIRSITEfoS OT*RVISE 11 33 Oft ON ZENO

20 TO a

10
T"It wMr.uwTT
S..T WCW COSTN OU. TIME V PEAK

02 To 3

2 IF £321 1S.138 200

if'023S

haft*

14 tS'. 4191

fmP~.
RTD (WLR) TM-63-Z

Ai~endix

The eqaeion with the present anmbers:

)
l 80 C-e16"63(1 -
Z/-41
T {.161 + .Z55e

137 e-C/zs 5 f + .050 f3} ('-)

re) a04S loglo e + . 3 Z( - f 1 ) (1 - 1z) lo 1 Ot + .04t-

fe = .5 *3 5 7 lIog,

"e 1 .975 P)
e

1 .0157
ez 45. (P4'"
AOJ -1 1 (e

'P
I~

I-
e3 160.

2e

3
RTD (WLR) IM-63-2

REFERENCES

1. Hllseurath. Klein. and Woofley. Table. of Tbenaod nmc Emoprttev

of Air Ip!I-idin Dsoiion an Iniato from 1. SOO~K to 15. 000.
MR--% AEDC TR 5940. D-cenJat19S9.

2. Gilmore. F. R.. llb=CU AMW WMd~~

ProeriesofAir to ?,: 006"L RAND. RU- 1543& Z4 Aivgust 195S.

"k
RTD (WLR) TM-63-2

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is (WL"p
1 (WLRJ)
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