Prog. Energy Comb. Sci.. Vol. 6. pp. 127 140.
00/0
@ Pergamon Press Ltd.. 1980. Printed in Great Britain.
SPREAD AND EVAPORATION OF LIQUID
F. BRISCOE and P. SHAW*
U KAEA, Safety and Reliability Directorate, Culcheth, Cheshire, Enffland
1. INTRODUCTION
The first stage in the development of many accident
sequences which lead to a major hazard (e.g. from fire,
explosion and toxic effects) is the release of hazardous
material from its containment and the consequent
generation of hazardous vapour. High potential haz-
ards are clearly presented by large quantities of
hazardous material which are usually stored and
transported in the liquid phase, either refrigerated at
low overpressure or pressurized at ambient tempera-
ture (n.b. some hazardous materials are also contained
under semi-refrigerated conditions).
The purpose of this paper is to discuss the charac-
teristics of hazardous material release and hazardous
vapour generation for both refrigerated and press-
urized liquid containment situations. Refrigerated and
pressurized containment will be considered separately,
since the characteristics of both release and vapour
generation are qualitatively different for the two
containment situations. Greater attention will be given
to refrigerated liquid containment, since the maximum
quantity of hazardous material stored in this form may
be an order of magnitude greater than that stored in
pressurized liquid containment.
2. REFRIGERATEDLIQUID CONTAINMENT
2.1 Release of Material
The main parameter concerning the release of
material from refrigerated liquid containment is the
rate of release. In some cases of catastrophic contain-
ment failure (e.g. spontaneous vessel failure, aircraft
impact on vessel, ship collision), the time-scale of total
release may be much shorter than the time-scale of
subsequent vapour generation, and the rate of release
may be assumed to be infinite (i.e. instantaneous
release mode). In other, more probable, cases of minor
containment failure (e.g. small missile impact, vessel
inlet/outlet pipe rupture), the time-scale of total release
may be comparable with the time-scale of subsequent
vapour generation and the rate of release must be
assumed to be finite (i.e, continuous release mode). The
finite value of the volume release rate f'c from a hole in
a containment vessel may be estimated using
= ACe 2gh + 0- ( p - p.))1/2
* Now with ICL, Business Systems Software Development,
Wilmslow, Cheshire, England.
0360 1285/80/0701 0127505.
where A is the cross-sectional area of the hole, Cn is the
discharge coefficient (which is equal to about 0,5 for a
circular hole), g is the acceleration due to gravity, p is
the density of the liquid, h is the height of the liquid/
vapour interface in the vessel above the hole, p is the
vapour pressure in the vessel, and p, is ambient
pressure. We are only interested in holes below the
liquid/vapour interface, since mass release rates from
the vapour space will be relatively small. Also, for low
overpressure refrigerated liquid containment, the
second term in Eq. (1) can be neglected and the flashing
phenomenon (described in Section 3) is insignificant.
Clearly, the maximum volume release rate occurs for a
hole at the base of the containment vessel and
decreases with time as h decreases.
2.2. Vapour Generation
The released liquid forms a pool on the surface
beneath the containment vessel. Two types of surface
are of interest, viz. ground surfaces such as concrete
and common soils (i.e. spillage on land), and water (i.e.
spillage on inland waterways and at sea). For spillages
of any liquid on ground or water, the total vaporiz-
ation rate at time t after the start of spillage is a
function of the pool area, which depends on the rate of
pool spread and the vaporization rate per unit area,
which usually depends on the rate of supply of latent
heat to the pool, i.e. a model for the prediction of the
total vaporization rate must take account of simul-
taneous spread and vaporization.
For spillages of cryogenic liquids (e.g. LNG with
Ta ~ - 161C, where Ts is the boiling point), the
dominant source of latent heat to vaporize the spill is
heat contained in the ground or water, For liquids with
higher boiling points (e.g. butane with Ta ~ -0.5C),
other sources of latent heat such as solar radiation and
heat stored in the atmosphere may also be important.
It is assumed that the rate of heat transfer into the pool
is the mechanism which limits the vaporization rates
per unit area of the liquids with boiling points below
ambient ground and water temperatures, i.e. the heat
absorbed by the pool is immediately utilized to
generate vapour through the boiling process. For
liquids with boiling points above ambient tempera-
(1) tures (e.g. oil), the situation is more complicated, since
the rate of surface evaporation is then the mechanism
which controls the vaporization rate per unit area.
We first consider the spread of liquids on ground
and water and then turn to the vaporization rates of
127
128 F. BRISCOEANDP. SHAW
FIG. 1A. Schematic diagram of liquid spread on land and water. Fa, FIL, F~w,Fsr and Fv represent the
gravity, liquid inertia, water inertia, surface tension and viscous drag forces respectively.
cryogens and liquids with boiling points below am-
bient temperatures on ground and water. The vaporiz-
ation rates of liquids with boiling points above am-
bient temperatures are not considered since these
liquids present the least potential explosion hazard
owing to their relatively slow vaporization rates.
2.2. I. Spread of liquids
The spread of a liquid pool on the fiat surface of
another solid or liquid medium is governed by the
conservation equations of incompressible fluid flow
(e.g. Refs 1, 2, 3). The main driving force for pool spread
is gravity. Although this force acts downwards, it
creates an unbalanced pressure distribution in the
pool, which causes the pool to spread sideways. The
force on a liquid element acts in the direction of
decreasing pool thickness and decreases with pool
thickness ; hence the gravity force decreases as the pool
spreads and becomes thinner. A second driving force
for pool spread may be the inbalance between the
surface tension forces at the liquid/air/ground or water
interface. The net surface tension force usually acts to
assist pool spread for the liquids of interest; and,
although it is usually smaller than the initial gravity
force, it does not decrease as the pool spreads and will
eventually become dominant. However, a final
surface-tension-driven regime of pool spread may only
be reached on smooth surfaces such as concrete and
calm water; for spills on rough ground and water, the
spill may reach a minimum pool thickness and cease to
spread or break up before the net surface-tension force
becomes significant.
The driving forces for pool spread are initially
counterbalanced by the inertial resistance of the liquid
to sideways acceleration. In addition, for spills on
water, the water beneath the spill will be set into
sideways motion and its inertia will contribute to the
5T - . ~
V .ml..--
/
/
total inertia. Indeed, for spills of a high viscosity liquid
(e.g. oil) on water, the inertia of the water will rapidly
become a significant part of the total inertia. Another
retarding force is the viscous drag on the spreading
liquid. Although this force is usually much smaller
than the initial gravity force, it increases as the pool
spreads and will eventually become important.
The action of these forces on a spreading pool is
shown schematically in Fig. la. Usually, three con-
secutive regimes of pool spread are distinguished: viz.
(1) a "Gravity-Inertia Regime" in which only the
gravity force FG and liquid inertia F~L are significant,
(2) a "Gravity-Viscous Regime" in which water inertia
Ftw and viscous drag Fv must also be taken into
account, and (3) a "Surface Tension-Viscous" Regime
in which surface tension Fsr replaces gravity as the
predominant driving force. Cryogenic liquid spills
vaporize relatively quickly and rarely reach the second
regime of pool spread, whereas spills of liquids with
boiling points up to ambient temperature may do so.
The third regime of pool spread is usually only
important for oil spills on water. Hence, we only
develop formulae for the first gravity-inertia regime of
pool spread. Equivalent formulae for the other two
pool-spread regimes may be found in Refs 2 and 3.
The formulae for the gravity-inertia pool spread
regime may be derived in the following approximate
manner rather than by a direct attack on the full
conservation equations of incompressible fluid "flow.
We assume that the spreading pool may be rep-
resented by a circular cylinder of radius r and uniform
height h, as shown in Fig. lb; then at time t
v = v, + f ' : m (2)
P
V
h = -- (3)
~r2
 Spread and evaporation of liquid 129

SPILL ON LAND SPILL ON WATER

..................... Jr ----'--

__ L',
-- / /
I
I
L aUID
L,OU,D
| I L
',fAh
r /

FIG. lB. Model representation of liquid spread on land and water.

where V is the volume ofliquid in the pool, V~represents
an instantaneous spill, Vcrepresents a continuous spill
and m is the mass of liquid which has been vaporized.
The equations which govern pool spread at time t are:
F a = FIL
i.e.
pnr2hoAh 1 2 d2r
r = e pr~r h-d-~
or
d2r Ah
--= -eg--
dt 2 r since the liquid will be exposed to different areas of
which may be integrated to give
dr
dt (egAh)l/2
with dr/dt = 0 at t = 0. The factor A = 1 for spills on
ground or (I - P/Pw) for spills on water where Pw is the
density of water takes account of the "effective height"
of a liquid pool on a water surface (see Fig. 1). The
factor e takes account of the fact that the liquid inertia
is equal to only a fraction 1/e of the inertia of the whole
liquid-pool mass moving with the acceleration at its
leading edge. The value of e can only be determined
accurately from a full analysis of the fluid flow; instead,
we have simply adopted the somewhat arbitrary
constant value of e = 2 which is greater than the value
of e = 1.34 derived theoretically in Ref. 2. Hence, the
model is conservative in the context of safety studies
since it overestimates fhe rate of pool spread and so
predicts an upper limit for the total vaporization rate
(which increases with pool area).
If the decrease in pool volume due to vaporization
(i.e. the m/p term in Eq. (2)) is neglected, eqs (2)--(4) may
be integrated analytically to give : for an instantaneous
spill of volume V/(m 3) and initial radius ro (m)
," = {to2 + ( ~ ) 1 / 2 t } t/2 (m)
and for a continuous spill at a rate V~(m3/sec}
( 32gA ~ l ' /4 ts/,
r = \~9-~n / (m). (6)
The case considered so far of symmetric pool spread
on a fiat surface covers most situations of interest (i.e.
unbounded spills or spills bounded by a circular
bound on level ground or water). There are also, of
course, other possible situations involving, e.g., asym-
metric confinement (e.g. a long straight wall) or spills
on sloping ground. In these cases, pool spread will be
asymmetric and the rate of vaporization will differ
from that predicted by a symmetric pool-spread model
ground or water surface and, in the case of spills on
sloping ground, the liquid will be exposed to ad-
ditional uncooled ground surface as the pool flows
(4)
bodily over the ground. It is usually possible to take
account of these effects, albeit often in an approximate
manner, by modifying the predictions of a symmetric
pool spread model.
2.2.2. Vaporization of cryogenic liquids on land
We consider first a pool of constant area, so that our
attention is concentrated on heat transfer rather than
pool spread. For cryogenic liquid spills on land, the
dominant source of latent heat to vaporize the spill is
heat contained in the ground. Initially, the heat flux
into the pool may be controlled by the rate of heat
transfer across a vapour blanket between the ground
and the liquid (i.e. film boiling condition). However, as
the surface temperature of the ground falls, the vapour
blanket collapses and allows better thermal contact
and faster heat transfer in the nucleate boiling con-
dition. The rate of heat flux into the pool is then
controlled by the rate of heat conduction through the
ground. Experimental evidence (e.g. Ref. 4) suggests
that the initial time period when heat transfer between
the ground and the liquid is the controlling mechanism
(5) is of fairly short duration ( ~ 10 sec). Hence, we have
developed a model based on the assumption that heat
130 F. BRISCOEANDP. SHAW

TABLE1. Thermal properties of concrete and soils

Density Specificheat Thermal conductivity Thermal diffusivity
Material p(kg/m3) Cp(J/kg-K) k(W/m-K) ~m2/sec)

Concrete 2300 961.4 0.92 4.16 x 10-7

Soil (average) 2500 836.0 0.96 4.59 x 10-7
Soil (sandy, dry) 1650 794.2 0.26 1.98 x 10-7
Soil (moist, 8~o water, sandy) 1750 1003.2 0.59 3.36 x 10-7

transfer through the ground is always the controlling
mechanism. This model is both simple and conserva-
tive in the context of safety studies, since it over-
estimates the rate of heat transfer during the first few
seconds and so predicts an upper limit for the vaporiz-
ation rate per unit area.
The model is based on the additional assumptions
that the liquid pool is thin and at a uniform tempera-
ture equal to its boiling point, that the pool is in perfect
thermal contact with the ground, and that heat
conduction in the ground is one-dimensional (vertical).
The governing equations and boundary conditions
are:
dT c32T
3 t = at3z---T
T=Ta for 0~<z~<oo at t=0
T=TB at z=0"~ for t>0
T=T~ at z=oo 3
where z is distance measured downwards from the
ground surface, T is the ground temperature and ~t is
the thermal diffusivity of the ground. The solution of
eqs (7) and (8) (after Ref. 5) is
T = T~ - ( T a - TB) erfc ( 2 ~ t )
so that the rate of heat flux into the pool #t is given by
#, = k ~ T _ k(Ta - TB) (W/m2)
6~Z z=O (nat) 1/2
where k is the thermal conductivity of the ground.
Finally, the mass vaporization rate due to this heat flux
is given by
m l = #_At = k(T~ - Ts) (kg/mZsec)
L l.,(nlxt) 1/2
where L is the latent heat of the liquid.
A difficulty in the application of this formula is the
choice ofappropriate values for the ground thermody-
namic properties. Some suggested values are given in
Table 1, and it can be seen that the moisture content is
an important parameter. Reference 6 provides more
detailed information on the variation of ground ther-
mal conductivity and diffusivity with moisture content
for different soil samples. Reference 6 also shows how
the soil and its moisture content can be treated
separately rather than as a single component; how-
ever, the single-component basis of eq. (11) is suf-
ficiently accurate for most purposes. Another difficulty
in the application of eq. (11) to spills on soils arises
from ground roughness, which gives an area of contact
surface greater than the pool area (nr2). We introduce a
multiplicative correction factor Z to allow for un-
certainties in ground thermodynamic properties, sur-
face roughness, and possibly other effects. Values of
Z ,,~ 3 are required to give good agreement between
theoretical predictions using average soil thermody-
namic properties and previous experimental data for
the maximum mass-vaporization rates of LNG spills
(e.g. Refs 4 and 6); and the same value of Z can
presumably be used with other cryogenic liquids,
although direct experimental confirmation of this
hypothesis would be worthwhile.
It should be noted that eq. (I1) indicates a mass-
(7) vaporization rate which decreases from infinity to zero
with time t as t- 1/2 In fact, as mentioned earlier, heat
transfer between the ground and the liquid limits the
(8) heat flux into the pool to a finite value at early times,
while other heat sources such as solar radiation and
the heat stored in the atmosphere maintain a finite rate
of heat flux at late times. Equations (11) and (12) below
can easily be extended to allow for these additional
heat sources if they are significant (see Section 2.2.4).
Figure 2a summarizes the possible heat transfer pro-
cesses, while Fig. 2b shows the transient variation of
(9) heat flux into a vaporizing liquid pool on land. A
further possibility is that energetic liquid release or
vigorous pool boiling leads to the formation of an
aerosol of small liquid droplets which vaporize quickly
(10) by absorbing latent heat from the atmosphere. An
extra term can also be included in eqs (1 l) and (12)
below to take account of this additional heat source,
which would act to increase the total rate of vaporiz-
ation, especially during the early stages of pool
vaporization when the air above the pool is still
(11) relatively hot. However, we do not feel that this
contribution is significant except in circumstances
which are especially favourable to both aerosol form-
ation and droplet dispersion into large regions of
relatively hot atmosphere (e.g. high velocity liquid
release from a containment vessel).
It is now possible to combine the pool spread eqs
(2)-(4) with an equation for the mass-vaporization rate
per unit area. The main difficulty is presented by the
fact that, for a spreading pool, successive annular
ground elements have been in contact with the liquid
for different time periods. The extension of eq. (10) to
allow for these different contact times gives
dm q, zk(Ta ~. Tn) ~m~ 2nr'dr_'
dt L L(n~) 1/2 go (t -- t') 1/2 (12)
 Spread and evaporation of liquid 131

SOLAR LONG-WAVE CONVECTION LATENT

RADIATION RADIATION FROM WIND N E A T LOSS

LIQUID . .~ /
/

FIG. 2A. Heat transfer processes for a vaporizing liquid pool on land.

where t' is the arrival time of the spreading pool at
radius r'. The complete model for the simultaneous
spread and vaporization of a cryogenic liquid on land
is thus eqs (2)--(4) together with eq. (12).
An accurate solution ofeqs (2)-(4) and (12) can only
be obtained numerically. However, an approximate
analytic solution can also be obtained by assuming
independent spread and vaporization (i.e. by neglect-
ing the m/p term in eq. (2)). One obtains the pool spread
formulae (eqs (5) and (6)) derived previously for
instantaneous and continuous spills, together with the
following formulae for the mass vaporized at time t:
for an instantaneous spill of volume V/(m s) and initial
radius ro = 0
completely vaporize the spill may be seriously in error.
Hence, we recommend the use of the simultaneous
numerical solution ofeqs (2)-(4) and (12) for cryogenic
liquid spills on land.
Some results obtained using the numerical solution
are now presented to illustrate the pattern of be-
haviour in four different situations, viz. :
(1) An instantaneous spill of 1000 m 3 L N G onto an
unbounded soil surface.
(2) As case (1), but with a circular bund at r = 40 m.
(3) A continuous spill of 10 mS/sec L N G for 100 secs
onto an unbounded soil surface, and
(4) As case (3), but with a circular bund at r = 40 m.

zk( T~ -- Ts) The variation of pool radius r and mass vaporized m

m= L(7~)I/2 X _(27~OVi)l/2f3/2 (kg) (13) at time t is shown in Figs 3 and 4. It can be seen that
there is little difference between the results for the
and for a continuous spill at a rate ~ (m3/sec) selected instantaneous and continuous releases of the
zk(T_TB ) (~)1/2 same total quantity, although an instantaneous release
m= L(nct)l/2 x t 2 (kg). (14) always vaporizes more quickly than a continuous one
of the same total quantity owing to its faster pool
However, a comparison of results obtained using spread rate. The presence of a circular bund has a
both the analytic and numerical solutions for the same pronounced effect in both cases (2) and (4); the time
situation (viz. an instantaneous spill of 1000 m 3 LNG, to completely vaporize the spill being extended from
Ref. 7) shows that the predictions of the analytic less than 212min for the unbounded situation to over 15
solution for important parameters such as the time z to min for the bounded situation.

HEAT FLUX (kW/m z)

z.00

300 ~ , ~ / / / N E A T CONDUCTION FROM GROUND (Eq(lO) l

200 I~IX
.ACTUALMEATFLUX
I00
SOLARRADIATION
+ MEATTRANSFERFROMATMOSPHERE
0 20 40 60 80 100 TIME (s)
FIG.2a. Transient variation of heat flux into a vaporizing liquid pool on land (values shown roughly apply to
LNG).
132 F. BRISCOEANDP. SHAW

11oi

loo

60

5o
E

40 A 0

2oi/
30 l A

D
iNSTANTANEOUS, BOUNDED AT r =40m
FINITE RATE (10rna/s FOR 100 sec-,SLUNBOUNDED
FINITE RATE (10reals FOR 100sec.~, BOUNDED AT r=40rn

lo

I ] I 1 I 1 I
20 40 60 80 100 120 140
t, secs
FIG. 3. Calculation of pool radius r at time t for a spill of 1000 m3 (416 tonnes) LNG on average soil.

2.2.3. Vaporization of cryogenic liquids on water
In analogy with cryogenic liquid spills on land, the
dominant source of latent heat to vaporize the spill is
heat contained in the water. Again, the initial rate of
heat flux into the pool may be controlled by the rate of
heat transfer between the water and the liquid or
possibly by boiling resistance due to lack of nucleation
sites. Experimental evidence (e.g. Refs 2, 8, 9, 10, 11)
suggests that the rate of heat flux into the pool rapidly
increases as the system moves from film boiling into
nucleate boiling conditions (n.b. the boiling transition
is often associated with ice formation for cryogenic
liquid spills on water). Furthermore, the rate of heat
flux into the pool quickly stabilizes and thereafter
remains constant, in contrast to the decrease of heat
flux with time for cryogenic liquid spills on land.
Table 2 summarizes the experimentally derived
values for this constant heat flux into the pool q2,
which have been obtained from LNG spills on water.
We take the maximum reported value (Ref. 11) to give
a conservative approach in the context of safety

TABLE2. Experimental data for LNG spills on water

Mass vaporization rate Spill size in pool

Experimenter per unit area (kg,/m2sec) spread experiments (m3)

USCG (i), Ref. 8 0.181 0.007-0.5

USCG OiL Ref. 9 0.155 small-scale(aquarium)
Shell, Ref. 10 0.024-0.195 small-scale(laboratory)
Esso, Ref. 11 0.195 0.8-10.8
 Spread and evaporation of liquid 133

INSTANTANEOUS, UNBOUNDED
A INSTANTANEOUS, BOUNDED AT r = L0rn
FINITE RATE (10rn31s FOR 100se~. UNBOUNDED
400
El FINITE RATE (10m~/s FOR 100 sea'S,
BOUNDED AT r = 4 0 m

300

200
g

100

, t / ~. J J L
0 20 1,0 60 BO 100 120 1/.0
t, sees
FIG. 4. Calculation of mass vaporized m at time t for a spill of 1000 m a (416 tonnes) LNG on average soil.

studies, i.e. q2 ~ 105 W/m2 for LNG. It should be
noted, however, that most of the experimental data is
derived from small-scale tests with calm surface con-
ditions. The action of waves in accident situations may
enhance the heat flux into the pool in the same manner
as ground roughness for spills on land.
It is tentatively suggested that the rate of heat flux
into the pool is proportional to the difference between
the ambient water temperature T~ and the boiling
point of the liquid Ts, so that the experimental data for
L N G can be extrapolated to other cryogenic liquids;
direct experimental confirmation of this hypothesis
would be valuable. With this assumption, we obtain
q: ~ 600(T~ - Ts) ~ 10,000 for L N G (W/m s)
dm
_ q2 ~ 6~L (T~ - Tn) ~, 0.2 for L N G (kg/m2sec).
dt L (1) for an instantaneous spill of volume V~(m 3) and
in importance as the pool spreads, in contrast to the
situation for cryogenic liquid spills on land.
The complete model for the spread and vaporization
of cryogenic liquid spills on water is thus eqs (2)--(4)
together with eq. (16). Again, an accurate solution of
the model equations can be obtained numerically and
an approximate analytic solution can be obtained by
assuming independent spread and vaporization. In
contrast to the situation for cryogenic liquid spills on
land, the analytic solution is usually sufficiently ac-
curate for cryogenic liquid spills on water (e.g. see Figs
5 and 6). The analytic solution comprises the pool
spread formulae (eqs (5) and (6)) derived previously for
instantaneous and continuous spills together with the
(15)
following formulae for the mass vaporized at time t :
(16) initial radius ro

Since the rate of heat flux into the pool does not 600
m-- (T _ Tn) ~rrr
r o2 t + ( 2 w A V i ) I / z t z } (kg) (17)
decrease with time, other heat sources do not increase L
134
KEY
(3 BURGESS ET AL
A LIND
o FAY
120
- x
100
80 V x
E
60
z,0
20
20 /,0 60
FIG. 5. Various model predictions for pool radius r at time t after an instantaneous spill of 1000 m a (416
tonnes) LNG on water.
(2) for a continuous spill at a rate I2, (m3/sec)
(600 T~, - T~) x 8(2ngA~)l/2ts/2
m = --L-
It should be noted that many other models have
been proposed to represent L N G spills on water. Some
early models were based on empirical formulae for
both pool spread-rate and the vaporization rate per
unit area derived from USCG experiments (viz.
Burgess et al., models (1) and (2), Refs 8 and 9) and Esso
experiments (viz. Lind model, Refs 11 and 12). While
we have retained an empirical formula for the vaporiz-
ation rate per unit area (viz., the Esso value, Ref. 11), we
believe that the empirical formulae for pool spread-
rates are inaccurate.
The main anomaly is that the empirical formulae are
independent of spill size; this discrepancy is pre-
sumably due to the small range of spill sizes in-
vestigated experimentally (i.e. 0.01-10 m 3 LNG, see
Table 2) and the weak dependence of the theoretical
formula on spill size (see eqs (5) and (6)). However, this
weak dependence has an important effect when the
experimental test conditions are extrapolated to ac-
cident situations perhaps 105 times greater in magni-
tude. A second discrepancy is the t 1/2 time-dependence
of the theoretical formula for an instantaneous spill
(see eq. (5)) and the linear time dependence of the
empirical formulae; this discrepancy is presumably
due to the small number of data points obtained in
most experiments (e.g. sometimes only two, or three
measurements of pool radius at different times), so that
the two time dependencies cannot be distinguished.
F. BRISCOEAND P. SHAW
RAJ / KALELKAR
x SHAW / BRISCOE (ANALYTIC SOLUTION)
SHAWl BRISCOE {NUMERICAL SOLUTION)
0 V
I I I I J J I
60 100 120 lZ.,0 160 1B0 200 220 2z,0
t, sec.~
The fact that the theoretical formula is based on
independent spread and vaporization, whereas the
(kg). (18) empirical formulae clearly take account of simul-
taneous effects, is not important since, as noted
previously, the analytic (i.e. independent) and nu-
merical (i.e. simultaneous) solutions are in close
agreement for L N G spills on water.
Further models have been based on the theoretical
pool-spread formula coupled with a formula for the
vaporization rate per unit area which has been theor-
etically derived using the assumption that a coherent
ice layer forms (e.g. Fay model, Ref. 13). Although ice
will certainly be formed, there is no experimental
evidence of coherent ice layer formation except in
small-scale aquarium tests (Ref. 8), and we believe that
"ice models" are not applicable to accident situations.
In any case, the predictions of the Fay model are not
significantly different from those of the theoretical
model developed in this paper. Finally, we mention the
Raj/Kaleikar model, which is similar to the one
proposed in this paper and has been developed on
behalf of the U SCG for use in future safety assessments
(Ref. 2).
Most of the proposed models have been reviewed in
Ref. 7 and are compared in Figs 5 and 6 for the case of
an instantaneous spill of 1000 m 3 L N G onto an
unbounded water surface. It should be noted that the
different results reflect different pool spread-rates,
since all the models are based on similar vaporization
rates per unit area. Figure 7 and 8 give results for the
same four cases that were compared for cryogenic
liquid spills on land, and it can be seen that the same
conclusions apply.
 Spread and evaporation of liquid
OX.V
400
300 - 0
o
200 -
1
100
0 " w L
100
t , 5ec5
FIG. 6. Various model predictions for mass vaporized m at time t after an instantaneous spill of 1000 m 3 (416
tonnes) LNG on water.
In summary, it should be noted that both pool
spread-rates and vaporization rates per unit area seem
less certain for cryogenic liquid spills on water than for
spills on land. However, most spills on water will be
unbounded whereas most spills on land will be
bounded, so that the time z to completely vaporize a
spill will generally be much shorter for spills on water
than for spills on land. Hence, calculations of sub-
sequent stages in the accident development will not be
sensitive to inaccuracies in the modelling of the spread
and vaporization of spills on water. Indeed, in safety
studies one often makes the assumption of instan-
taneous total vaporization of spills on water, although
an estimate of final pool area perhaps based on
minimum pool thickness enables more accurate calcu-
lations of the subsequent vapour-cloud dispersion.
2.2.4. Other h a z a r d o u s liquids
Models of the spread and vaporization of other
liquids with higher boiling points are similar to those
135
KEY
(9 BURGESS ET AL (~)
BURGESS ET AL (11)
A LIND
0 FAY
V RAJ / KALE'L. KAR
X SHAW / BR1SCOE
(ANALYTIC SOLUTION )
S H A W / BRISCOE
N UI'4E RICAL SOLUTION)
200 300
developed for cryogenic liquids, except that the heat
flux into the pool must be modelled more accurately.
The most important additional heat sources are solar
radiation and the heat stored in the atmosphere.
The additional heat flux due to radiative heat
transfer q3 is given by (after Ref. 14)
q3 = ( 1 - fl)S 9- e.ataTa~ - eptrT~ (W/m 2) (19)
where fl is the albedo of the pool surface (i.e. the
fraction of the incident solar radiation S which is
reflected by the pool surface), tr is the Stefan-
Boltzmann constant, cot and ep are the emissivities of
the atmosphere and pool respectively, and T,t and Tp
are the temperatures of the atmosphere and pool
respectively. The first term represents the absorption
of direct solar radiation while the other two terms
represent long-wave radiative heat exchange between
the atmosphere and the pool. The accurate calculation
of q3 requires detailed meteorological information,
and in safety studies one often makes use of simple
136 F. BRISCOEAND P. SHAW

INSTANTANEOUS, UNBOUNDED

INSTANTANEOUS, BOUNDED AT r=40m

110 FINITE RATE (IOm3/s,DURATION 100 secC)~ UNBOUNDED

FINITE RATE(IOm~/s DURATION 100 secJ),

BOUNDED AT r = L,Om

100

90

80

70

60

o~ 50
aJ

Z,O [3 &

3O

20

10

i
0 20 /,lO 610 810 i
100
i
120
i
l&O

t. sees

FIG. 7. Calculation of pool radius r at time t for a spill of 1000 m 3 (416 tonnes) LNG on water.

conservative estimates of q3 (e.g. qa will usually be less
than 1000 W/m2).
Convective heat transfer leads to an additional heat
flux into the pool which can be estimated by examining
heat transfer across the thermal boundary layer above
the pool surface, or by examining mass-transfer across
the mass boundary-layer above the pool surface, and
then applying the heat/mass transfer analogy (e.g. Ref.
15). The second indirect approach has been utilized in
Ref. 14; but we prefer the first direct approach, which
has been utilized in Ref. 6. After considerable simplifi-
cation, the additional heat flux due to convective heat
transfer q4 is given by (after Ref. 6)
q4 = 7.2(Tair- Tp)u'a23r -'177 (W/m 2) (20)
where T,i, is the ambient air temperature and u is the
wind speed. It can be seen that q4 increases with
temperature difference and wind speed but decreases
with pool radius. This latter effect is due to the increase
of the thermal boundary-layer thickness and con-
sequent decrease of the temperature gradient across it
with increasing distance from the windward edge of the
pool.
The models for the spread and vaporization of
liquids with boiling points up to ambient temperature
are, then, eqs (2)--(4) together with versions ofeqs (12)
and (15) for spills on land and water respectively, which
have been extended to include the additional heat
fluxes q3 and q4 into the pool.
Some illustrative results are presented for four
situations, all involving instantaneous spills of 1000 m 3
butane onto an average soil surface; viz. :
(1) A spill with high solar radiation (800 W/m2),
high air temperature (15C), high wind speed (7 m/sec)
and low ground temperature (5C), onto a surface with
a circular bund at r = 40 m.
 Spread and evaporation of liquid 137

(2l As case (1), but with a spill onto an unbounded
surface.
(3) A spill with low solar radiation (50 W/m2), low
air temperature (5C), low wind speed (2 m/sec) and
low ground temperature (5C), onto a surface with a
circular bund at r = 40 m.
(4) As case (3), but with a spill onto an unbounded
surface. It can be seen from Figs 9 and I0 that the times
z to completely vaporize the spills will be considerably
longer than for the equivalent L N G spills (see Figs 3
and 4), especially for cases (3) and (4) with low heat flux
into the pool.
It should be noted that the heat flux from the pool
(i.e. latent heat losses, the third component of q3, and
possibly heat transfer into the ground or water) may
exceed the heat flux into the pool (i.e. the first two
components of q3 and q4) in some circumstances for
liquids with boiling points near to ambient tempera-
ture such as butane. In this case, the pool temperature
Tp falls below TB, and further vaporization is controlled
by evaporation from the pool surface. This latter
phenomenon is driven by the vapour pressure dif-
ference across a mass boundary-layer in the same way
that convective heat transfer is driven by the tempera-
ture difference across a thermal boundary-layer,
whereas the models developed in this paper are based
on the assumption that heat absorbed by the pool is
immediately utilized to generate vapour through the
boiling process. Surface evaporation is of course the
mechanism which applies to liquids with boiling
points well above ambient temperatures (e.g. oil).
However, as mentioned previously, these liquids
present the least potential explosion hazard, so that
surface evaporation will not be explored in the present
paper.

iNSTANTANEOUS, UNBOUNDED

& INSTANTANEOUS, BOUNDED AT r = 40 m

(b FINITE R A T E (10rn3/s, D U R A T I O N 100 sec.~ ), U N B O U N D E D

El FINITE RATE(10m~'/s,DURATION 100 sect).

BOUNDED AT r = L 0 m
400

300

Ln

o
200L

100

OI ~ I I L t I I
20 40 60 80 100 120 1~0
tsecs

FIG. 8. Calculation of mass vaporized m at time t for a spill of 1000 m 3 (416 tonnes) LNG on water.
138 F. BRISCOEANDP. SHAW

SEE SECTION 2 . 2 4 FOR DETAILS OF: TNE FOUR TEST CASES:

O CASE (i) - NION CONVECTION , RADIATION :BOUNDED

B CASE (d) - NIGH CONVECTION ,RADIATION UNBOUNDED
0 CASE .,ii) - LOW CONVECTION , RADIATION BOUNDED

A CASE (iv} - LOW CONVECTION ,RA[3~ATION :UNBOUNDED

300

E
200

100

o 0 o. 0 o 0 o

I I I 1 - - [ I I
0 100 200 300 400 500 600 700
t,sec$

FIG. 9. Predictions of pool radius r at time t a~er a spill of 1000 m3 (612 tonnes) butane on average soil in
various weather conditions.

3. P R E S S U R I Z E D LIQUID CONTAINMENT generated by the flashing process can be obtained by

The release of hazardous material from pressurized
liquid containment is more complicated than that
from refrigerated liquid containment. When a press-
urized containment vessel fails, a rarefaction wave
travels from the point of failure into the vessel
contents. The effect of this wave on a liquid element is
to relieve the initial pressure and set the liquid in
motion towards the point of failure. The main compli-
cation arises from the fact that the liquid element is
superheated with respect to the lower pressure and
may boil spontaneously. This process is usually known
as flash vaporization or flashing, since it occurs very
rapidly. The latent heat required to vaporize a fraction
5 of the liquid is taken from the fraction (1 - 6) which
remains in the liquid phase, so that the liquid cools as
vaporization proceeds. Clearly, flash vaporization will
cease if the temperature of the liquid component falls
to its boiling point at the prevailing pressure. Hence,
an upper limit to the amount of vapour which may be
equating the latent heat required to vaporize the
fraction 5 to the sensible heat initially stored in the
fraction (1 - 5) above the final pressure boiling point
of the liquid. Taking the initial temperature of the
liquid to be the ambient air temperature T~ and the
final pressure of the liquid to be the ambient air
pressure p~ gives "'
6.,~. = C p ( T . - TB) (21)
a + Cp(T~ - Ta)
where Cp is the specific heat of the liquid. For example,
for propane with Cp ~ 2260 J/kg-K, L = 430 kJ/kg, To
--- 15C and Ta = - 4 2 C ; fimax= 0.23. However, this
amount of vapour is rarely generated owing to dy-
namical considerations, viz. boiling resistance due to
lack of nucleation sites and the need to transfer heat
into growing vapour bubbles.
The rate and nature of the release depends on the
type of vessel failure. Catastrophic failure or minor
 Spread and evaporation of liquid 139

failure below the liquid/vapour interface in the vessel
lead to the rapid release of the entire contents as a two-
phase mixture with flashing both in situ and as the
mixture emerges from the vessel. However, even for
failure in the vapour space at the top of a containment
vessel, it is believed that the liquid froths up so that an
initial stage of pure vapour release is again followed by
the release of the remaining contents as a two-phase
mixture. Following violent release from the contain-
ment vessel, a further fraction of the remaining liquid
may vaporize as small liquid droplets rapidly absorb
latent heat from the atmosphere. Large liquid droplets
which fall to the surface beneath the containment
vessel without vaporizing completely, together with
any liquid release which is directed downwards, form a
spreading liquid pool which subsequently vaporizes in
the same way as the spills from refrigerated liquid
containment discussed in Section 2.
It is possible to model the release of flashing liquids
from pressurized containment vessel in great detail.
However, the time-scales of vapour generation by the
flashing process and heat transfer from the atmosphere
to small liquid droplets are very short compared to the
time-scales of subsequent vapour cloud dispersion.
Hence, in safety studies one often makes the assump-
tion of instantaneous vapour generation for the release
of hazardous material from pressurized liquid
containment.
The main difficulty concerns the estimation of the
fraction of the vessel contents which is vaporized
and the size of the resultant vapour cloud. Some
relevant experiments have been carried out in which a
mechanical lance or small explosive charge was used to
induce the catastrophic failure of small pressure vessels
containing 0.2-10001 of propylene at a pressure of 22-
39 bar and a temperature of 50--80C (Ref, 16). In some
tests, the entire vessel contents vaporized very rapidly,
but-it is interesting to note that the maximum fraction

10 s

10 ~
E

10 z .. I I I I I _ I l
0 100 200 300 LO0 500 600 700
t ,sec~

FIG. 10, Predictions of mass vaporized m at time t after a spill of 1000 m 3 (612 tonnes) butane on average soil
in various weather conditions.
140 F. BRISCOEANDP. SrIAW
of the vessel contents which subsequently combined
with flammable concentrations of air was 0.7 and that
only about 4 0 ~ of this propylene (i.e. about 0.3 of the
total vessel contents) contributed to the generation of
explosive pressure waves when the vapour cloud was
ignited; this effect is apparently due to the inhomo-
geneous nature of a vapour cloud, which has been
partly generated by the vaporization of discrete liquid
droplets. Because of these results, there is at least one
official recommendation (Ref. 17) that safety studies
should make the conservative assumption that release
from pressurized liquid containment involves instant-
aneous vaporization of the entire vessel contents, but
that only half of this quantity is available for a vapour-
cloud explosion. On the other hand, analyses of the
Port Hudson incident (Ref. 18), when liquid propane at
ambient temperature was released from a fractured
pipeline, suggest that, although a significant fraction of
the release vaporized very quickly, the remaining
liquid fraction was sufficient to erode a crater of depth
over 1 m and with a diameter of about 3 m.
4. CONCLUDING REMARKS
In summary, it is our belief that the first stage in the
development of an accident sequence, (viz. the stage
involving the release of hazardous material and the
generation of hazardous vapour) is relatively well
understood compared to some of the later stages in the
accident sequence. It would certainly be worthwhile to
remove some relatively minor inadequacies in present
knowledge, especially those concerning experimental
values of the vaporization rates per unit area for a
greater range of materials on both land and water.
However, most of the major scientific uncertainties
(e.g. those concerning the discrepancies between for-
mulae for pool-spread rates on water and the detailed
understanding of release from pressurized contain-
ment) do not have a critical effect on calculations
concerning later stages of the accident sequence, and
simple conservative assumptions can be used to over-
come the scientific uncertainties in current safety
studies.
Acknowledgement--Some of the results quoted in this paper
were obtained in connection with a contract for the Health
and Safety Executive. However, the views expressed in this
paper are those of the authors and they do not necessarily
reflect the viewsor policy of the Health and Safety Executive.
(Manuscript received 5 December 1979)
REFERENCES
i. LANDAU,L. D. and LIFSHITZ,E. M., Fluid Mechanics,
Volume 6 of Course on Theoretical Physics, Pergamon
Press, London (1959).
2. RAJ,P. P. K. and KALELKAR,A. 5., Assessmentmodels in
support of the hazard assessment handbook, U.S. Coast
Guard Report No. CC-D-65-74, January (1974).
3. RAUSCH,A. H., KUMAg,R. M. and LYNCH,C. J., A critical
technical review of six additional hazard assessment
models, U.5. Coast Guard Report No. CC-D-54-77,
March (1977).
4. BURGESS,D. S. and ZABETAKIS,M. G., Fire and explosion
hazards associated with liquefied natural gas, U.S.
Bureau of Mines Report of Investigations No. 6099
(1962).
5. CARSLAW,H. 5. and JAEGER,J. C., Conduction of Heat in
Solids, Clarendon Press, Oxford (1959).
6. American Gas Association, Project IS-3-1, LNG Safety
Program Interim Report on Phase II Work, Battelle
Columbus Report, July (1974).
7. SHAW, P. and BRISCOE, F., Vaporization of spills of
hazardous liquids on land and water, UKAEA Report
SRDRIO0 (1978).
8. BURGESS,D. S., MURPHY,J. N. and ZABETAKIS,M. G,
Hazards of LNG spillage in marine transportation, U.S.
Bureau of Mines Report No. NTIS AD-705078 (1970).
9. BURGESS,D. S., BIORDI,J. and MURPHY,J. N., Hazards of
spillage of LNG into water, U.S. Bureau of Mines Report
No. NTIS AD-754498(1972).
10. BOYLE,G. J. and KNEEBONE,A., Laboratory investigation
into the characteristics of LNG spills on water.
Evaporation spreading and vapour dispersion, Shell
Research Limited, Report of work done for American
Petroleum Institute (1972).
I 1. McQUEEN,W., WHIPP, R. H. and MAY,W. G., Spills of
LNG on water--vaporization and downward drift of
combustible mixtures, Esso Research and Engineering
Company Report No. EE61E-72, Report of work done
for American Petroleum Institute (1972)
12. LIND,C. D., Explosion hazards associated with spills of
large quantities of hazardous materials, Phase I, U.S.
Coast Guard Report No. NTIS AD-AO01242 (1974).
13. FAg, J. A., Unusual fire hazard of LNG tanker spills,
Comb. Sci. Tech. 7, 47-49 (1973).
14. MACKAY,D. and MATSUGU,R. S., Evaporation rates of
liquid hydrocardon spills on land and water, Can. J.
chem. Enong., 51 (1973).
15. TREYBAL,R. F., Mass Transfer Operations, McGraw Hill,
New York (1953).
16. MAURER,B., HESS,K., GIESBRECHT,n. and LEUCKEL,W.,
Modelling of vapour cloud dispersion and deflagration
after bursting of tanks filled with liquefied gas, 2nd Int.
Syrup. on Loss Prevention and Safety Promotion in the
Chemical Process Industries, Heidelberg (1977).
17. GEIGER, W., The impact of pressure loads due to gas
explosions on nuclear power plant, Battelle Frankfurt
Report BF-R-62.968-1 (1977).
18. BURGESS,D. S. and ZABETAK1S,M. G., Detonation of a
flammable cloud following a propane pipeline break,
U.S. Bureau of Mines Report of Investigations 7752
(1971).