CORRECTED COPY

Kinetics, S i o i c n i o ~ ~ r rznd
y Heat
E f f e c t s -.
f o r the Fire L X D O S U ~
in6uced I ne r r c l Docori?osi t i on of

Re:

Glycols

Ethyl

Kinetics, s;ojchiorztry

a n d h ~ r ~t f i e c tf o~r t k i i r c fxposur?

inductc: t n ~ r m ~cjeconposi
l
ti:ofi of g i h y l ~ nglycols
~
h r v e b2r, ~elrr&:ln=.;f roa
~ v e f l t b i ea a t ~ .

-.

Hydroxyl contain5ng compcunds (ylycois, ~ i y c o lether:, pci yols)

rcpidly and ~ x o i h e r a i c z ; l y deconpcsc t o f o n n o n - c o n d ~ n s i ~gcses
l ~ upon
hzaiing. Pressures of several thousand p s i g hcve been o b s e r v d i n closcci
vessel s . Soiilo of thesz corr$ounds dtc~;n@os?~i 'impera trrres b~!ow t n ~r i n o ~ e l
boilins point.

During 2 f i r e ex3osur2 s i t u t t i o n , t n ~b o i l i n g ilmpErzture of E

vessel w
i
t
h
- t high safety r g i f e i prts:jure can exce& t h e decori~osi;ion i e q e r e t u r g . I h i 5 m e ~ a r z n d ~ i id; o c ~ z e n t sour b e s t e s i i i i z i t k i n e t i c s , s t o i c n i o ~ t r yznd
h e z i ~ f i c c t sf o r the f i r e Exposurc induce^ thzrriil ritcomposition of t i l e ethylen5
~ l y c o l sES dptormined from d a t c f o r anslcoous compounds.

The ~ t h y l e n e.glycols Ere known t o do,conpcs~E ? or brior.: t n ~ri

n = \ r d l b o i i f n ~points.1 Tilt jailing points znd t e n p e r c t u r e s o f i n t i c i t i ~ c s z ~ 3 s i t i c nhave been r e p o r t ~ iz c foilowr:

.:-

.:"

.-

.
!

r.

0.

.f.L

i
I

t
.'A%'

i;.

.-

. ..,>.-'

'

< -.

.-!/v

f j
,4

.- .

-he 1ower t e m ? e r ~ t u r e s of

I
ini t i a1 oeconrposi tion were d e t e r s i n e d by very
s e n s i t i v e pressure measurements . I The higher temperGures werc oeirriiiined
c s i ng t h e O i f f e r e n i i a l Scanning tel &inlet& (DSC )4
l i m i t s of ind;lstrjally s i g n i f f cant d ~ a ~ p c r s i t i o r , .

.*p/L-

-4

DECO!4POS!i ION ST01CH1014ETRY

'

--T

Polyeth_vlene glycol Cecornpos2s t o f o r n non-conoensi b1 e gzs (1ess

v o l a t i l ~ s )and m i s c ~ l l a n e o u sorgznics
than 0.1 p e r c e n t by weight of t h e
having an averrgf m l e c u l e r w~iahto f c p p r o x i r z t e l y 50.5

L .

Ethylene glycol decomposes t o iorin two l i q u i d l a y e r s and s o m ~

The decomposiiion products o f diethylene glycol ~ l s oconsisi cf two l i q u i d
l a y e r s and some non-condensible gas. The l i q u i d s have been ioentf f i e d cs weter
and hxdrocarbons H a wide b o i l i n g range .6
gas.

Methyl , Ethyl and Butyl Cellosol ve and Carbi t o l s decompose e t 700C

t o f o r n i m i x t u r e of hydrogen, wster, methene, e t h y l e n e , ethane and carbon
monoxide with t n average molecular w e i ~ h to f 20-22 I b / l b mole,,

Since sziety valve s i z e i s a i r e c i l y proportional i o t h e squire roo;

of t h e flowing molecular w e i g h t , a conservative value of 20 I b / l b mole s h o u l d
be used f o r the ethylene glycols.
f

DECOMPOSITION KINETICS

F i r s t o r d e r k i n e t i c s , d e r i v e d 'frm t h e a v ~ i l a b l epolyethylene oxide

(polyethylene olgcol ) aecomposiiion dsta , a r e 2s fo1lows:S ,8
R(ppn)

where

1.2321 76 E+16 exp ( - 4 5 53S/ (RGAS*TK))*\.!

2Gp.S

TK

- Deconposi t i o n rr t e

(pph)

Universzl C z s f o f i s t e n t (1 - 9 8 7 2 c ~ I / g I i in!Ile
Temperature ( O K )
- h'eight ( I h )

OK)

2.7 ro 5.5 T i i i i t s f e j r e r t h ~ ni h se:onC

~
anti
~ 5 isn e r e f o r ? u-j
r z > r g s t f i : c K Z X ~ ~ Uf iZk ~ l i n o o gr z T 2 f o r ihE U ~ C Z E ~ ~ ~
decomposition of ~ t h o x y i ~ tproducts.
?
f n e f i r s - ; ~ , x p r e s c i o r ;c i v s s t~:

oiycol z t 400eC sn+r;loes

Die:nyienr
i n rwo hours. 5

ksune:

zimss:

Z ? <

c o m p i ~ r ~de:mp3sicior,
,

Dieihyi en^ Cigco; Frrciion LE-eining 4 SOOOi

(673:i5O~) 3 f r g r t w c hours

= exp (-kt)

Assum: A c t i vstion Energies ere i d e n t i c t l f o r tne kco;;i?csiti on

.
Ethylene Glycols
of poi ye thy lea^ E l y c ~ itnc'
2.3025S = k 0 ex:, ( 4 5 3 3 6 / (1 .9972

*- 73.1 5 ) )

R (p?h) = 1.3556 Eel 5 exp (-45536/ (RG!.SfT~))iW

Rec2nt MC d s t r 1 0 f o r t h a decomposition o f i e t r r e i h y i e n e glycol give
En e c t i v a t i o n en-.rgy of 46205 c t l / g n mole O K . T h i s value i s consist en^ w i t n chf
zbovn k i n e t i c s wbjch mey be usei t o r q r e s s n i t h e u n c ~ t ~ l y z eCde c o ~ p o s i t i o no f
the ethylene glycols'
EAT

OF DECOMPOSITION

T ~ hEe a i o f oecompcsition of polyethylene glycol hzs bson r z p o r t e d

t o be e n d o i h c m i c . 1 ) I no hzzt of deconposi t i on of tetraeThylene glycol , c z i c u i ~ t ~ d
. This value may be used f o r i h ~
from ARC deta,lO is hpproxirztely
decomposf i i o n of t h e e t h y l en5 g i y c m
-3

A ccnvenignt wcy t o ExprizsS t h e i'neszal s t ~ b i l i i yOC 2 pclyzzr i s

tnrouah the v ~ i u r I h , which i s tnf CtmperEiurf z i which t'ne p o l y n ~ rlcsss h ~ i f
of i t s wcjcji;; i n 25 minutes of h ~ z t i n f includiog 2 f i v ? minute hsat-u? p ~ r i ~ d .
-.
r ne Th v a l uf f o r polyethyl2n? glycol i s 3 ~ 5 " c . : Using in9 k i n ~ i i c scescribed
above, the c-lcuizted f r a c t i o n s r e i x i n i n g (??tor 33 minutes a t 3 @ j 0 CE r e ES f0i-icws:

Ethylene Eiycols

-the

kinetics for the o e ! : c ~ p o s ~ t i o nc f E Z : ? ~ ~ E ciycols

~E
?rzsf5sgc:

i n t h i s rremcrr~nduiilEpDe27 rztsontble Czsc6 on eviilable d i t ~and z r e reccritcnd~f

for sizing s a f e t y relief.