..
25 2550
1
Accidental Release Risk Assessment
. .
1
(Accidental Release Risk Assessment)
(
)
1)
2) (,,)
 : ,
 :
3)
4)
1.
2.
3.
2
4.
4
1.1
4 1) 2)
3) 4)
1 2
1.1
1
 2 20
 10 100
 20 200
 20 200
 20 200
 20 200
 40 400
 100 1000
2
 100 1
1
 100 1
3
 2 20
 5 50
 5 50
 5 50
 50 500
 500 5000
 500 5000
 1000 10000
3
4
 15 150
 20 200
1.34
 30 300
 50 500
0
o
3
 21
o
10000 100000
3
 500 5000
 500 5000
1.2



()
1.3
1.4




4
WHAZAN( World Bank Hazard Analysis) DEGADIS, SLAB
1 /
F
1.5
1.2
(over pressure, )
4 90%
7
14 ()
35
(
) 4 7
714
14
5
1.6
1.3
()%
(/) 10% 50% 100%
1.6 500 1300 3200
4.0 150 370 930
12.5 30 80 200
37.5 8 20 50
1.7
()
1.8
" " "fault tree"
4
1.4
2x10
5
( 3 ) 1x10
5
( 3 ) 1x10
6
3x10
3
3x10
4
6
3x10
3
7x10
3
1x10
4
1x10
2
/
1x10
2
/
3
7
2
1
1.1 (SourceTerm Analysis)
(release scenario)
(physical state of the chemical)
1
1
Physical & Chemical
Properties:
System Conditions: Environmental
Conditions:
Molecular weight
Vapor pressure
Heat capacities
Boiling point
Latent heat
Substance quantity System pressure
System temperature
Size and orientation of release point
Spill area
Mitigative measures
Ambient temperature
Wind speed
Ground temperature
Humidity
2
(single or twoPhase of a pure compound or mixture).
(liquefied gas)
2
Singlephase gas jet (choked or unchoked) 1. (
)
2.
3. (No condensation)
Twophase gas jet
(choked or unchoked)
1.
()
2.
8
3.
(rainout)
liquid pool
Twophase liquid 1. Rupture in pressurized storage vessel
below liquid level.
1.
)
2.
3. (flashes)
vapor cloud liquid pool.
Liquid spill pool 1.
2.
Cryogenic liquid spill 1.
(refrigerated storage vessel)
2.
Choked flow release
Flashing emissions
vapor cloud liquid pool
1.2. EXPERT Model
EXPERT Model





 pool

9
1
1
(gas liquid) single
twophase
10
. TwoPhase Releases (Gas and Liquid)
2 (TwoPhase Releases) 5 (LowVolatility Liquid
Release)
1
2 TwoPhase Releases
11
. SinglePhase Gas
EXPERT
(noncondensing gas release) 3
choked unchoked
3 NonCondensing Gas Release
12
. SinglePhase  High Volatility Liquid
Highly Volatile Liquid
EXPERT
4 Highly Volatile Liquid
13
. SinglePhase  Low Volatility Liquid
5 EXPERT Low
Volatility Liquid Release pool
pool dike bund
EXPERT pool
= 1
5 LowVolatility Liquid Release
14
1.3 Choked Flow for Gas Releases
(p*) ideal gas
) 1 (
s
*
1
2
p
p
+
=
: = specific heat (C
p
) specific heat
(C
v
)
p
s
= , Pa
p
a
= ambient pressure
p
*
p
a
, choked p* < pa nonchoked p*
Pascals (Pa) standard atmosphere 101325 Pa.
choked
1.4 Emission Rate
EXPERT
1.4.1. TwoPhase Gas Release (Choked)
2 choked
flow choked flow T* critical
pressure
=
*
*
T
1
Tb
T
R
M
exp Pa 325 . 101 p
M = molecular weight (kg/kmol)
= heat of vaporization Tb (J/kg)
R = gas constant = 8314 J/kmol K
Tb = normal boiling point (K)
T* = temperature choked (K)
vapor choked flow conditions (F*)
+ =
*
s
s
s
p
*
*
p
p
ln R
T
T
ln MC
M
T
1 F
15
:
C
p
= gas heat capacity T
s
(J/kg K)
T
s
= (K)
enthalpy (H*) choked flow
H
*
= C
p
(T
s
T
*
) + (1  F
*
)
choked flow density choked
flow conditions (*)
1
l
*
*
*
* *
F 1
M p
RT
F
=
l
= liquid density T
b
(kg/m
3
).
choked flow parameters
2
1
l
*
p
p
*
* o
F 1
D
fL 4
1
H
) 85 . 0 ( 2 A E
=
:
E = emission rate (kg/s)
A
o
= (m
2
)
f = 0.0045, estimated (dimensionless)
L
p
= (m)
D
p
= (m)
1.4.2. TwoPhase Gas Release (Unchoked)
2
H = enthalpy (J/kg)
rel
= density (kg/m
3
)
2 unchoked
16
2
1
p
p
rel o
D
fL 4
1
H
) 85 . 0 ( 2 A E
=
:
E = emission rate (kg/s)
A
o
= (m
2
)
f = 0.0045, estimated (dimensionless)
L
p
= (m)
D
p
= (m)
1.4.3. TwoPhase Pressurized Liquid
2 Two
Phase Releases pressurized liquid
0
orifice
equilibrium flow
(Lp/Le 1)
2
1
pl
s
2
s
s
o
NC
T
RT
Mp
A E
=
:
E = emission rate (kg/s)
A
o
= (m
2
)
M = molecular weight (kg/kmol)
= heat of vaporization Tb (J/kg)
R = gas constant = 8314 J/kmol K
e
p
pl
3
s
2
l a s
2
s
L
L
C ) RT ( C ) p p ( 2
) Mp ( R
N +
=
T
s
= (K)
p
s
= (Pa)
C
pl
= liquid heat capacity T
s
p
a
= (P
a
)
l
= liquid density T
b
T
b
= normal boiling point (K)
17
C = discharge coefficient, 0.6 (dimensionless)
L
p
= (m)
L
e
= equilibrium flow (m), assumed 0.1 m
equilibrium flow
L
p
/L
e
> 1, the expression becomes:
2
1
pl
s
2
s
s
o
C
T
RT
Mp
F A E
=
F = a pipe friction factor
+
=
p
p
2
D
fL 4
1
1
F
f = 0.0015, estimated (dimensionless)
D
p
= (m)
1.4.4. TwoPhase Refrigerated Liquid
TwoPhase Releases 2
2
1
2
s
s
s pl
2
l sv s
2
o
RT
Mp
T C
F
) p p ( C 2 A E
+ =
:
E = emission rate (kg/s)
A
o
= (m
2
)
M = molecular weight (kg/kmol)
= heat of vaporization Tb (J/kg)
R = gas constant = 8314 J/kmol K
T
s
= (K)
p
s
= (Pa)
C
pl
= liquid heat capacity T
s
l
= liquid density T
b
T
b
= normal boiling point (K)
C = discharge coefficient, 0.6 (dimensionless)
P
vs
= vapor pressure T
s
F = a pipe friction factor
18
+
=
p
p
2
D
fL 4
1
1
F
f = 0.0015, estimated (dimensionless)
D
p
= (m)
1.4.5. SinglePhase Gas Release (Choked)
T NonCondensing Gas Release
3
2
1
) 1 (
) 1 (
s s o
1
2
p CA E
+
=
+
E = emission rate (kg/s)
A
o
= (m
2
)
p
s
= , Pa
p
a
= ambient pressure
C = discharge coefficient, 0.75 (dimensionless)
= specific heat (C
p
) specific heat
(C
v
)
1.4.6. SinglePhase Gas Release (Unchoked)
NonCondensing Gas Release
3
[ ]2
1
a s s o
) p p ( 2 KYA E =
:
E = emission rate (kg/s)
A
o
= (m
2
)
s
= density (kg/m
3
)
p
a
= (Pa)
2
1
C
K
=
) 35 . 0 41 . 0 (
p
p p
1 Y
4
s
a s
+
=
19
C = 0.62
2
= A
o
/A
1
A
1
= crosssectional area
1.4.7. SinglePhase Liquid Release (High Volatility)
Highly Volatile Liquid 4
high volatility liquid
liquid pool BREEZE HAZ
models
2
l s s a h
gH ) p , p max( p + =
p
h
= (Pa)
p
a
= (Pa)
s
= density (kg/m
3
)
g = acceleration gravity (9.806 m/s
2
)
H
l
= (m)
p
s
= the vapor pressure T
s
(Pa)
M = molecular weight (kg/kmol)
= heat of vaporization Tb (J/kg)
R = gas constant = 8314 J/kmol K
T
b
= normal boiling point (K)
[ ]2
1
a h s o
) p p ( 2 KA E =
A
o
= (m
2
)
2
1
C
K
=
C = 0.65
2
= A
o
/A
1
20
A
1
= crosssectional area
1.4.8 SinglePhase Liquid Release (Low Volatility)
:
E = emission rate liquid (kg/s)
T
rel
= liquid (K)
low Volatile Liquid 5
high volatility
evaporating pool (Epool)
vh
v
p
75 . 0
a
2
2
7
pool
p
p
M A U ) ) 15 . 273 T ( 0043 . 0 1 ( 10 94 . 6 E + =
E
pool
= pool (kg/s)
U
r
= 10 (m/s)
A
p
= pool (m
2
)
M = molecular weight (kg/kmol)
T
2
= T
rel
T
a
(K)
Ta = (K)
[T
2
273.15] = 0 [T
2
273.15] < 0
p
vh
= vapor pressure of hydrazine T
2
(Pa)
+ =
2 2
2
vh
T 0061557 . 0 ) T ln( 22 . 8
T
2 . 7245
8580 . 76 exp p
p
v
= vapor pressure T
2
(Pa):
= heat of vaporization T
b
(J/kg)
T
b
= normal boiling point (K)
R = gas constant = 8314 J/kmol K
T
2
2 Epool T
2
E
pool
EXPERT hydrazine
E
pool
< E, pool E
pool
> E
E, pool (A
p
)
E
pool
= E
21
1.5 (Release Temperature)
EXPERT
The BREEZE HAZ
density
dense gas
plume
EXPERT
1.5.1 TwoPhase Gas Release (Choked)
2
F
rel
= flash fraction of chemical of interest (dimensionless)
T
*
= temperature choked conditions (K)
F* = mass vapor fraction choked conditions (dimensionless)
Frel < 1, ClausiusClapeyron equation:
=
rel b
s
T
1
T
1
R
M
exp Pa 101325 P
:
T
rel
= release temperature (K)
M = molecular weight (kg/kmol)
= heat of vaporization at T
b
(J/kg)
R = gas constant = 8314 J/kmol K
T
b
= normal boiling point (K)
p
a
= ambient pressure (Pa)
Frel 1,
pl
*
* rel
C
) F 1 (
T T
+ =
:
= heat of vaporization at T
b
(J/kg)
C
pl
= liquid heat capacity at T
s
(J/kg K)
1.5.2 TwoPhase Gas Release (Unchoked)
ClausiusClapeyron equation:
=
rel b
s
T
1
T
1
R
M
exp Pa 101325 P
:
T
rel
= release temperature (K)
22
M = molecular weight (kg/kmol)
= heat of vaporization at T
b
(J/kg)
R = gas constant = 8314 J/kmol K
T
b
= normal boiling point (K)
p
a
= ambient pressure (Pa)
1.5.3 TwoPhase Pressurized Liquid
TwoPhase Gas Release
(Unchoked).
1.5.4 TwoPhase Refrigerated Liquid
TwoPhase Gas Release
(Unchoked).
1.5.5 SingePhase Gas Release (Choked)
2 :
choked flow (adiabatic reversible temperature change) 2
choked flow conditions ambient pressure conditions (adiabatic but not reversible).
+
=
1
1
85 . 0 1 T T
s rel
:
T
rel
= release temperature (K)
T
s
= storage temperature (K)
= specific heat (C
p
) specific heat
(C
v
)
1.5.6 SinglePhase Gas Release (Unhoked)
3
E = emission rate (kg/s)
choked flow
[ ] ) aT 4 1 ( 1
T 2
T
s
s
rel
+ +
=
2
o a p
MA p
ER
C 2
1
a
=
E = emission rate (kg/s)
A
o
= area of hole(m
2
)
p
a
= ambient pressure (Pa)
23
M = molecular weight (kg/kmol)
T
s
= storage temperature (K)
R = gas constant = 8314 J/kmol K
C
p
= gas heat capacity at T
s
(J/kg K)
1.5.7 SinglePhase Liquid Release (High Volatility)
4
normal boiling point
1.5.8 SinglePhase Liquid (Low Volatility)
5
pool boiling point
1.6 Vapor Fraction Calculations
two
phase release singlephase releases
1)
2) high volatility liquid
3) low volatility liquid evaporation.
twophase releases (vapor fractions)
= 1
1.6.1 TwoPhase Gas Release (Choked)
2
T
rel
= (K)
T
*
= temperature choked conditions (K)
F* = mass vapor fraction choked conditions (dimensionless)
:
+ =
) T T ( C
F F
rel * pl
* rel
:
= heat of vaporization at T
b
(J/kg)
C
pl
= liquid heat capacity at T
s
(J/kg K)
1.6.2 TwoPhase Gas Release (Unchoked)
2
T
rel
= (K)
24
:
+ =
a
s
rel
s
p
rel
rel
p
p
ln R
T
T
ln MC
M
T
1 F
:
M = molecular weight (kg/kmol)
= heat of vaporization at T
b
(J/kg)
R = gas constant = 8314 J/kmol K
C
p
= gas heat capacity at T
s
(J/kg K)
P
s
= (Pa)
p
a
= ambient pressure (Pa)
change in enthalpy storage conditions ambient
conditions (H)
) F 1 ( ) T T ( C H
rel rel s pl
+ =
1.6.3 TwoPhase Pressurized Liquid
2
T
rel
= (K)
=
) T T ( C
F
rel s pl
rel
= heat of vaporization at T
b
(J/kg)
T
s
= storage temperature (K)
C
pl
= liquid heat capacity at T
s
(J/kg K)
1.6.4 TwoPhase Refrigerated Liquid
2
TwoPhase Pressurized Liquid
1.7 Initial Concentration Calculations
dense gas plume
3
f
a
= molar fraction of air
f
w
= molar fraction of water vapor
f
i
= molar fraction of chemical of interest
25
singlephase gas release volatility liquid release.
boiling point condensation occurs,
vaporizing flashing f
i
= 1 fa fw = 0
f
a
+f
w
+f
i
= 1
molar fractions
temperature (T) (K) 370 K saturated molar fraction water
vapor (e
s
) 1 atm
T
2353
3994 . 6 e log
s
=
molar fractions 298 K, 0.03
energy
molar fraction water vapor
s w
e
100
RH
f =
RH = relative humidity %
.
1.7.1 SinglePhase Gas Release
3 f
i
= 1 = 0
1.7.2 SinglePhase Liquid Release (Low Volatility)
5
T
rel
= release temperature (K)
a
v
i
p
p
f =
:
p
v
= vapor pressure T
rel
(Pa)
p
a
= ambient pressure (Pa)
1.8 Density Calculations
density
T
rel
= release temperature (K)
F
rel
= initial mass vapor fraction of chemical of interest (dimensionless)
f
i
= initial molar fraction of chemical of interest (dimensionless)
26
f
a
= initial molar fraction of air (dimensionless)
f
w
= initial molar fraction of water vapor (dimensionless)
density
p
a
= ambient pressure (Pa)
R = gas constant = 8314 J/kmol K
M
a
= molecular weight of air (kg/kmol)
M
w
= molecular weight of water (kg/kmol)
density
:
MT = mean molecular weight (air, water vapor, chemical) (kg/kmol)
1.9 Release Diameter Area
:
u = exit velocity
E = emission rate
s
= density in the container
A = hole emission area
1.9.1 LowMomentum Release
27
E = emission rate (kg/s)
rel
= release density (kg/m
3
)
Release Diameter Area
D
rel
= diameter (m)
U
r
= ambient wind speed (m/s)
1.9.2 HighMomentum Release
rel
= release density (kg/m
3
Release Diameter Area
D
rel
= diameter (m)
D
s
= hole or stack diameter (m)
s
= density at hole (kg/m
3
)

28
2
.
1) Wind Speed and Direction
2) (atmospheric stability)
PasquillGifford stability classes 6 (A F) 3
4
3 PasquillGifford
4
2.1 Dense Gas Releases
A cloud from a dense gas release behaves very differently than a plume from a
lighterthanair release. Because the gas is heavier than air, the cloud characteristics are
primarily gravitydriven. Negative buoyancy and stable density stratification are among the
factors that prevent the application of a Gaussian dispersion model from accurately simulating
a dense gas release.
When a dense gas is released in nonaerosol form, it falls toward the ground. If the
release begins as a vertical upward jet, the plumes rise is halted by the effects of gravity and
it turns downward as it moves downwind. Whether the gas is released at ground level or it
29
falls to the ground, the cloud slumps when it first hits ground level. The momentum of the
fall causes the center to dip while the edges bulge. The cloud then bounces back to
resemble a layered flattened cylinder in which the vertical dimension is a minor fraction
typically 1/20th to 1/50thof the horizontal dimension. This pancakeshaped cloud elongates
and spreads as the wind flow moves it along and ambient air becomes entrained in the cloud.
Whether or not a jet is involved, a dense gas release often requires modeling a secondary
pool of liquid as the source of the dense gas cloud.
In aerosol form, the cloud may exhibit some Gaussian dispersion characteristics, except that
the cloud falls to the ground rapidly and then travels along the ground in the same manner as
a nonaerosol dense gas release.
A dense gas release may begin at a temperature significantly below ambient, either
as a result of a release of a gas refrigerated to a liquid or as a result of the sudden
depressurization of a container storing gas as a liquid. The cloud is affected by heat transfer
from air and the underlying surface. Heat released by condensation of atmospheric water
vapor can also be important. An aerosol cloud is likewise affected by heat energy changes
between the aerosols two phases.
To determine whether your scenario must be run using a dense gas model, refer to the
section on calculating the Richardson Number Working with BREEZE HAZ. There are three
types of releases to which the Richardson number applies: instantaneous (that is, occurring
over a few seconds) and continuous (that is, lasting several minutes with little or no variation
in emission rate) groundlevel releases and continuous jet releases. For an instantaneous
release, a Richardson number greater than 700 indicates a dense gas. For a continuous
dense gas release, the Richardson number should be greater than 32. If the Richardson
number does not fall within these parameters, you should consider using another model (for
example, AFTOX, SCREEN3, ISC3, INPUFF) for a passive release.
2.1.1 Evaporation Model
BREEZE HAZ DEGADIS+, SLAB, and AFTOX use the same evaporation models.
Since the EPAs DEGADIS model does not have the capability to directly model liquid spills,
Trinity developed a seamless interface between the dispersion model and the following
evaporation models: 1) the Vossler steadystate energy balance model16; 2) the Shell Oil
Companys evaporation model used in their SPILLS model17; and 3) the Clewell evaporation
model18.
During a liquid release, it is assumed that a liquid pool will be formed on the ground after the
chemical exits the original container. BREEZE HAZ calculates the evaporation rate and
initializes DEGADIS+ or SLAB as a groundlevel release.
30
All three methods of determining evaporation rates require the saturated vapor pressure (VP).
Depending on a setting in the chemical database, one of six formulae is used to compute the
vapor pressure:
Antoine1 equation from AFTOX (A, B and C constants required)
31
32
When the constants are not available, the liquid density value in the database will be used. If
no values are available, the model assumes a liquid density of 1 g/cm
3
. V
c
is the critical
volume and is included in the database.
The following sections provide additional information on each the evaporation models.
2.1.2 Vossler Model
The Vossler evaporation model is a steadystate model in which the pool temperature
is adjusted based on the net energy input into the pool from all possible sources. The pool
temperature is used to determine evaporation rate. These sources of energy include solar
radiation (Q
sol
), longwave radiation emitted by the pool (Q
pol
) and the atmosphere (Q
atm
),
convective heat transfer from the atmosphere (Q
he
), heat conducted from the ground (Q
grd
),
and heat loss due to evaporation (Qev). The steadystate temperature is the temperature at
which the sum of all sources of heat (energy) transported into the pool exactly balances the
heat transfer out of the pool; that is, the sum of energy terms described above is zero. The
steadystate energy balance is expressed as:
where:
Q
total
= 0 at steady state
Many of these energy terms can be expressed as a function of the pool surface temperature.
The equation is solved iteratively for the pool temperature, which is then used to calculate
evaporation rate. The evaporation rate is proportional to the mass transfer coefficient at the
liquid poolatmosphere interface and the vapor pressure of the chemical, both of which are
functions of the pool surface temperature.
This Vossler model requires detailed chemical property information. Currently, only three
chemicals in the chemical database have the properties necessary to use this model: nitrogen
tetroxide, hydrazine, and dimethylhydrazine.
2.1.3 Shell Model
In the Shell model, the evaporation rate is primarily a function of the forced convection over
the liquid pool due to the wind. It is assumed that there is no heat transfer due to evaporative
cooling or radiation, and that the pool temperature is the same as the air temperature. The
evaporation rate (Q) is equal to:
where:
S
h
= the Sherwood number
D = the Molecular diffusion coefficient
v
= the vapor density
L = the pool width
33
For turbulent flows (Re > 320000), the Sherwood number is equal to:
For laminar flows (Re < 320000), the Sherwood number is:
where:
Sc = the Schmidt number
Re = the Reynolds number
The Schmidt number is given by v/D, and the Reynolds number by uL/v,
where:
v = the kinematic viscosity of air in m
2
/sec
u = the wind speed at 10 m above ground level in m/sec
The molecular diffusion coefficient, D, is equal to:
where:
binary diffusivity (D) = is in cm
2
/sec
T = the temperature in (K)
MA and MB = the molecular weights of the chemical and air
P = the pressure in atmospheres
AB
= the hard core diameter of the binary pair
D
= the collision integral for diffusion.
The collision integral
D
is calculated from the expression
where:
A1 and B1 = are constants obtained by curve fitting calculated values of
D
versus T*
T* = the temperature reduced by the potential well depth
AB
T* may be expressed:
The chemical database includes
A
which is approximately equal to 1.15 times the boiling point of
the chemical.
34
In the molecular diffusion coefficient (D) equation,
AB
is equal to
2.1.4 Clewell Model
For those chemicals for which only the molecular weight and vapor pressure are known, the
Clewell evaporation model is used. This model is a crude approximation to the Ille and
Springer model, which is similar to the Vossler model. The model is represented by a single
formula:
35
2.1.5 Release Duration
For a sourceterm model, the words instantaneous and continuous normally describe the
manner in which the chemical gets out of the container. For a nonsourceterm model, the
words instantaneous and continuous describe the manner in which the chemical enters the
atmosphere. In some models (that is, DEGADIS+), the emission rate into the atmosphere can
be time varying.
The BREEZE HAZ models also allow a finite duration release. A finite duration release is one
that only exists for a limited period of time. That is, a finite duration release is neither
instantaneous, nor does it go on without ceasing. For example, if a relief valve opened and
the entire contents of the vessel escaped in 15 minutes, a finite duration release of 15
minutes would have occurred. If a model allows a finite duration release, the actual time of
duration (rather than specifying an instantaneous or continuous release) should always be
used.
To decide whether the release should be considered continuous or instantaneous two factors
need to be known: 1) the release duration, and 2) the location of the nearest receptors or the
maximum distance to the lowest concentration of interest. To determine the category, if a
concentration of interest is specified, the release first needs to be simulated as a continuous
release. Then the travel time to the maximum distance of the concentration of interest is
compared to the actual release duration. If only receptor locations are of interest, their
distance from the source can be substituted for the maximum distance of the concentration of
interest.
36
In practice, a continuous release initially should be assumed. The time required for the
material to reach a specific downwind distance is then compared to the actual emission
duration. If the emission duration is longer than the time it took for the material to reach a
downwind point, the release may be considered continuous. Otherwise, the release should be
considered instantaneous.
The travel time (t
trav
) to some site at a downwind distance (x) from the release site can be
approximated using this formula:
where:
u = ambient wind speed
If the model allows a finite duration release, the release duration should also be compared to
the desired averaging time. If the release duration is less than the averaging time of concern,
then a transient model should be used to reflect average concentrations more accurately. For
example, if the release duration is 5 minutes and the averaging time of concern is 15 minutes,
it is important to use a finite duration model to simulate the proper average concentrations.
2.1.6 Averaging Time
Hazardous chemical releases are often of short duration, and the concentrations of
interest are shortterm averages. Typical concerns from a hazardous air release are the
maximum shortterm concentration and the maximum dose. Many hazardous air pollutant
models are designed to provide concentration predictions for unit averaging times ranging
from 1 second to 1 hour.
BREEZE HAZ models can typically provide concentration estimates for userspecified
averaging times of 1 hour or less. Due to entrainment with ambient air, a dense gas release
typically does not remain significantly dense for travel times longer than 1 hour.
Meteorological input, however, is often based on an hourly average. To determine the
appropriate averaging time, the user should examine the release duration and the
concentration levels of concern (keeping health or other reference levels in mind).
If a concentration exposure to population is of concern, the averaging time should be
determined from the concentration limit selected. For example, Short Term Exposure Limits
(STEL) have an implicit time interval of 15 minutes, the Immediately Dangerous to Life and
Health limit (IDLH) has an implicit interval of 30 minutes, and the Emergency Response
Planning Guideline (ERPG) concentrations have a 60minute implied exposure time. If
flammability or possibility of explosion is of concern, the averaging time should be on the
order of seconds since an ignition can occur when the instantaneous concentration is within
the flammable limits of the chemical.
37
Defining an appropriate averaging time for dense gas modeling applications is complicated.
Large averaging times allow for more plume meander, and therefore, lower average
concentrations. Thus, a 5minute ensemble average concentration is generally less then a 1
minute ensemble average since more meander can generally occur in 5 minutes than in 1
minute. Thus, some researchers use much shorter averaging times (510 seconds) than the
release duration, especially when comparing model predictions with field measurements when
these field measurements are made with shorter averaging times. However, meteorological
input (that is, stability classification) used in conjunction with these models is based on a
longer duration, usually 60 minutes.
The time scales relevant to determining the averaging time to be used in the models can be
designated as:
t
haz
= averaging time associated with the hazard being assessed
t
rel
= duration of the contaminant release into the atmosphere
t
trav
= travel time from the release site to a receptor
If t
a
is the averaging time that represents the effect of plume meander, then the largest
recommended t
a
is the minimum of t
haz
, t
rel
, and t
trav
(for steadystate or transient releases);
smaller values of t
a
can be chosen to compare with field observations or to obtain a
conservative estimate of downwind impacts. If t
a
,t is the averaging time that accounts for
transient effects (not pertinent for steadystate releases), t
a
,t is recommended to be t
haz
.
When the averaging time used is less than the requested averaging time, or may be
the same when using AFTOX, the output must be converted to represent the requested
averaging time. To extrapolate from a reported average concentration to the requested
averaging time, multiply the reported average concentration by the ratio of the actual
averaging time to the requested averaging time. This means that to find a concentration
averaged over the requested time, a higher concentration may need to be found in the output.
For example, if the release duration is 500 seconds and the requested averaging time is 1000
seconds, the averaging time of 500 seconds should be used. To convert the concentrations
reported in the output to concentrations for the requested averaging time, each reported
concentration must be multiplied by (500 s/1000 s) or 0.5. This means that if a 1000 second
average concentration of 1 ppm is of interest, the output will have to be searched for a
concentration of (1 ppm/0.5) or 2 ppm.
An alternative to average concentrations being used to determine impact is the use of dose.
Dose is an indication of total exposure at a point. It is usually expressed in units of ppm
minutes.
The simplest dose (D) calculation is given by:
38
where:
C = concentration (ppm)
t = time (min)
t
0
= time the release began (min)
Some expressions for dose give an increased weighting to the chemical by raising
the concentration to some power N (change C to CN in the above equation). In the simple
dose calculation, N has the value of one. When N is not equal to one, dose should actually
be referred to as toxic load or some other name since the units would no longer be ppm
minutes. The values of N for the chemicals in this document are:
Species N
Ammonia 2
Chlorine 2
Ethylene Oxide Not available
Hydrogen chloride 1
Hydrogen fluoride 1
Sulfur dioxide 1
2.1.7 Evaporating Pool
For an evaporating pool release, the source area is the area of the evaporating pool.
If the source area A
p
is not known, it can be calculated from the effective evaporation rate
(regression rate) W
p
using the identity:
where:
E
pool
= emission rate (kg/s)
v
= vapor density of the source material at the boiling point temperature T
BP
W
p
= the known evaporation rate expressed as a velocity (m/s)
The vapor density
v
is given by the ideal gas law is:
where:
M = the input molecular weight of the source material
P
a
= the ambient atmospheric pressure (Pa=101325. N/m
3
)
R = the gas constant [R=8.31431 J/(molK)]
T
b
= the input boiling point temperature
39
2.1.8 Jet Releases
For a jet release, the source area is the area of the source after it has fully expanded
and the pressure is reduced to the ambient level. If the source material is stored and released
as a pure vapor, it is recommended that the expansion be treated adiabatically. The source
area A
rel
is expressed as:
where:
P
s
= the storage pressure
P
a
= the ambient atmospheric pressure
T
rel
= the input source temperature
T
s
= the storage temperature
A
o
= the actual area of the rupture or opening
When the source material is stored as a liquid under pressure and released as a two
phase jet, A
rel
is the area of the source after it has flashed and formed a liquid dropletvapor
mixture of the pure substance.
In this case the value of A
rel
is given by the formula:
where:
l
= the input liquid density of the source material
A
o
= the actual area of the rupture or opening
m
= the density of the liquidvapor mixture after flashing and at the boiling point temperature
T
BP
with liquid mass fraction.
The value of
m
is calculated from the equation of state and with some rearranging of sterms
is given by:
where:
F
l
= the input initial liquid mass fraction
l
= the input liquid density of the source material
v
= the vapor density of the source material at the boiling point temperature.
A liquid dropletvapor mixture is assumed to form when the material is stored as a
liquid under pressure at a temperature T
s
above the boiling point temperature Tb and the
material is rapidly released due to a container rupture. These temperatures are used to
estimate the mass fraction F
l
in the liquid phase using the equation:
where:
40
C
psl
= the specific heat of the material in the liquid phase
= the heat of vaporization at the boiling point temperature T
BP
2.1.9 Instantaneous Releases
For an instantaneous release, the source area is the area of the volume source in the
ground plane centered on the point X = Y = Z = 0.0. The source area A
rel
is defined to be:
where:
V
rel
= the volume of the instantaneous release
H
rel
= the height of the volume
E
t
= the input mass of the release
v
= the initial density of the release
When the source is a pure vapor release,
v
is the vapor density of the pure
substance at the source temperature T
s
and is given by
When the source is liquidvapor mixture,
v
is the mixture density
m
at the boiling
temperature with liquid mass fraction.
41
3 (Fire Modeling)
3.1 Confined Pool Fire Model Theory
A confined pool fire occurs when liquid is ignited in a confined area such as a dike or
a tank. The dike may be circular or rectangular. The vapor required to sustain the flame is
provided by the liquid, which vaporizes as a result of ground heating and radiation from the
flame.
The Confined Pool Fire model contains two calculation modules:
Calculation of radiation at various specified distances from the center of the pool fire, and
the distance to various specified radiation levels. These radiation levels could be the 5 kW/m
2
level specified by the US EPA in the 112(r) RMP regulations2, or the radiant flux levels
specified in the US federal standard 49 CFR 193.2057 for LNG facilities.
Calculation of the dynamic temperature rise of a nearby structure, such as a neighboring
tank wall or structured steel column, exposed to the thermal radiation from a fire in a tank or
dike.
3.1.1 Pool Fire Geometry
The dimensions of the flame are characterized by the flame diameter, the flame
length and the flame tilt. For confined spills, the flame diameter is determined by the
confinement (e.g., dike, tank) dimensions. In the presence of wind, flames near the ground
surface tend to be dragged thus increasing the downwind dimension. Flame drag, flame
length and flame tilt are a function of wind velocity, the spill diameter and the fuel burning
rate.
3.1.2 Liquid Burning Rate
At steady state, a fraction of the combustion energy generated by a burning liquid
goes into vaporizing the fuel necessary to maintain the fire. Experimental data show that, for
any liquid burning in a pool, the burning rate increases with pool diameter up to a point.
Eventually, the liquid will burn at a constant rate. From Mudan and Croce (SFPE Handbook):
where = fuel liquid density (kg/m
3
)
H
c
= net heat of combustion (J/kg)
42
and H
v
= latent heat of vaporization (J/kg)
c
p
= liquid specific heat (j/kg K)
T = liquid storage temperature (K)
T
b
= boiling point (K)
Thus, the steady state mass burning rate of any liquid fuel in any size pool is given by:
Since experimental data for are only available for a few compounds, a value of 0.3 m1 is
used for all materials except LNG and LPG.
For LNG and LPG, special correlations based on experimental data are used.
For cryogenic liquids burning on water (unconfined pool fires only), the burning rate is
increased due to the additional heat transferred from the water to the boiling liquid. The rate
of heat transfer is a function of the water temperature, the boiling point of the cryogen, the
degree of turbulence at the interface, etc. This rate must be determined experimentally. In the
absence of experimental data, for cryogenic liquids, the mass burning rate calculated by the
previous equation is multiplied by two for unconfined spills on water.
For LNG, the mass burning rate
43
3.1.3 Flame Length
The flame length, L
f
, of a pool fire is a function of the pool diameter, the burning rate and the
ambient air density. The following correlation proposed by Thomas is used to determine the
flame length to diameter ratio:
These correlations were based on experimental wooden crib fires. Brown7 confirmed that
these correlations were applicable to LPG and LNG pool fires.
For rectangular fires, the flame is assumed to be a parallelepiped prism. The flame lengths of
rectangular fires are calculated using an equation identical to the one described above, with
the exception that the width of the rectangular pool, W, is used instead of the diameter, D.
3.1.4 Flame Tilt
Pool fires are often tilted by the effect of wind, and under strong winds, the flame
base may be dragged in the downwind direction. The flame tilt angle, , is measured from
the vertical and is a function of the wind velocity, the pool size, and the burning rate. To
determine the flame tilt, the following correlation proposed by AGA is used:
44
For, a rectangular fire, the angle of tilt is calculated using the same correlation, with the width
of the rectangular pool used instead of the diameter D.
3.1.5 Flame Drag
The flame drag, D', represents an extension of the flame base downwind, beyond the
confines of the pool, while the upwind edge of the flame and the flame width remain
unchanged. Downwind targets, relatively closer to the flame surface, would receive a
significantly higher radiation level than estimated.
The effect of flame drag on square and rectangular fires is to increase the flame base
in the direction of the wind. The flame shape remains rectangular, and, because of the
reduced distance to the target, the thermal radiation in the downwind direction would
increase. For circular flames, the flame shape changes from circular to elliptical.
Flame drag is a function of the pool diameter and the wind speed. The following
correlation developed by Moorhouse is used to predict flame drag for circular fires:
Although the above equation was developed by Moorhouse for fires in rectangular dikes with
low aspect ratios, it was examined by Mudan and recommended for the prediction of drag
from circular fires, with D and D' substituted for W and W'.
For fires in rectangular dikes, the following correlation is used.
3.1.6 Thermal Radiation
45
As noted previously, the thermal radiation intensity, q", incident upon a target away
from the flame is calculated from:
This requires that the emissive power of the flame (E), the view factor (F) and the
transmissivity () be calculated.
3.1.7 Maximum Emissive Power
The flame surface emitted power, E, is the total radiative power leaving the flame
surface per unit area, and may be computed from Stefan's Law, which relates the radiative
power of a hot body to its average black body temperature. The emissive power leaving the
outside surface of a fire may be approximated by:
E = E
b
where = emissivity of the flame
E
b
= the maximum black body emissive power (kW/m
2
)
For LNG, the maximum black body emissive power has been found to be about 190
KW/m
2
. For hydrocarbons heavier than LNG, large pool fires produce black soot, which
effectively masks the flame and reduces the effective maximum black body emissive power.
The British Institute of Petroleum recommends the use of 50 kW/m2 for the maximum surface
flux from LPG flames. Experimental data collected by Mudan and Croce suggest a maximum
value of 158 kW/m. This high value is more in line with data recorded by Shell during large
scale fire tests. The higher values may be attributable to sootless flames generated by LPGs
with a high content of propane, while the lower values may be attributed to LPGs with a high
concentration of butane. Because of the large variation in the recommended values of
maximum flux from LPG fires in the literature, and in the absence of reliable experimental
data, a mole fraction weighted average is suggested for use in calculating the maximum
emissive power of any LPG.
where x = mole fraction of propane in LPG
This equation gives a maximum flux of 158 kW/m
2
for pure propane and 50 kW/m
2
for pure
butane.
3.1.8 Flame Emissivity
The emissivity of the flame, , accounts for the fact that the flame is approximated
as a gray emitter, and is not an ideal black body radiator. For a black body, the emissivity
equals 1. For a gray body, the emissivity is less than 1. The emissivity of a homogeneous gas
mixture with path length or thickness, x, is given by the following relation:
46
If the luminous flames were regarded as being spectrally gray, i.e., k
m
= km, this equation
becomes:
= (1 exp [  k
m
x] )
where k
m
= extinction coefficient (m
1
). Suggested values are 0.3 m
1
for LNG and 0.335 m
1
for LPG
x = path length or flame thickness (m)
This is the equation used in this model to calculate the flame emissivity.
3.1.9 View Factor
The view factor is a measure of the solid angle that the target makes with the
emitting surface. It is a function of the size and the shape of the flame, as well as the
distance between the flame and the target. If the target sees nothing but the emitting surface,
the view factor is equal to one. If the target cannot see the emitting surface at all, F is equal
to 0. For a partially filled view, F ranges between 0 and 1. The following expressions derived
by Mudan were used to compute the view factors from a cylindrical flame to vertical and
horizontal area elements:
47
The following expression for the view factor to a horizontal receiving element from a tilted
rectangular flame is used in this model:
Since, there are no explicit equations for the vertical view factor from a tilted rectangle, the
above equation was used to compute the vertical view factor after modifying the coordinate
system, as suggested by Mudan.
When the horizontal and vertical elements of the target see the same portions of the flame,
the maximum view factor, F
max
, is the vectorial sum of the vertical and the horizontal view
factors and is given by :
At certain locations downwind of the flame (e.g., when the target is under a tilted flame), the
horizontal and vertical elements of the target do not see the same portions of the flame. In
such cases, the use of the vectorial sum to calculate the maximum view factor is not correct.
To calculate the maximum flux, the target was gradually tilted by one degree, beginning from
the position where the target saw the whole flame. View factor calculations were then made
until the maximum value was found.
3.1.10 Atmospheric Transmissivity
Atmospheric transmissivity, , is the fraction of radiant energy emitted by a flame that
is not absorbed by water vapor, dust and carbon dioxide that may be present between the
flame and the target. The magnitude of transmissivity depends on the spectral distribution of
the flame radiation, the length of the path to the target and the composition of the
atmosphere. Absorption by carbon dioxide in the atmosphere is negligible. For conservative
48
calculations, the presence of suspended dust in the air is also neglected. However, water
vapor absorption may be significant during high humidity days.
The transmissivity of water vapor can be calculated, given the distance between the flame
and the receiving object, the temperatures of the flame, the receiver and the intervening
atmosphere, and the relative humidity. The numerical method of calculating the transmissivity
of water vapor was obtained from the program appended to the A.G.A. report 8 based on
research conducted by General Dynamics.
3.1.11 U.S. Federal Code 49 CFR 193.2057 for LNG Facilities
The confined pool fire model can be used to calculate the exclusion distances to the four
radiant flux levels specified in US federal standard 49 CFR 193.2057. This code is applicable
to LNG facilities only. The target classifications specified by the code, and the corresponding
allowable incident radiation fluxes at these targets are reproduced in Table 5. Iterative
calculations are made at the userspecified ambient conditions and target height to determine
the distances at which these flux levels occur.
3.1.1
2
Dyna
mic Temperature Rise Calculations
49
Dynamic temperature rise calculations are used to predict the temperature rise when
a thermally thin structure is exposed to radiation or impingement from a pool fire caused by
an accidental release of a liquefied fuel gas. These calculations are divided into two main
categories.
1. Target located at a distance from the flame
2. Flame impinges on one side of the target
Each of these categories is further divided into four sub categories:
a. Uninsulated vertical target
b. Uninsulated horizontal target
c. Vertical target with perfect insulation on the side away from the flame
d. Horizontal target with perfect insulation on the side away from the flame
For a target located at a distance from the flame, the variation of surface temperature with
time is given by the following differential equation
The values K
1
, K
2
and K
3
assume different values based on the sub category and are
summarized in Table 6. When the flame impinges on the target, the following differential
equation is used to compute the unsteady state temperature profile:
where T
f
= flame temperature (K)
3.2 Unconfined Pool Fire Model Theory
An unconfined pool fire occurs when a spreading pool of liquefied fuel gas ignites. If
the release of the liquefied fuel gas is continuous, the diameter of the flame will increase with
50
time until the rate of fuel supply is equal to the rate of burning. For instantaneous releases,
the diameter will reach a maximum before it diminishes as the fuel burns. As in the case of
confined pool fires, in the presence of wind, flames near the ground surface tend to be
dragged thus increasing the downwind dimension. Flame drag, flame length and flame tilt are
a function of wind velocity, the spill diameter and the fuel burning rate. The same basic
equation that was used in the confined pool fire model to determine the radiation flux level at
any point is also used here. The shape of the flame is assumed to be cylindrical.
3.2.1 Liquid Pool Size
The pool diameter depends upon the nature of the released material, the release
volume, release duration, the maximum liquid burning rate and the nature of the substrate.
Pool size also depends on whether the spill is continuous or instantaneous. Heat transfer
from the ground plays an important role in determining the pool size. If the pool has ignited,
the incoming radiation from the flame also contributes to the determination of the pool size.
3.2.2 Unconfined Continuous Releases
The spreading of a continuously released liquefied gas on a flat, nonpermeable sub
soil is calculated by the following equation:
where r = radius of the spreading pool (m)
t = tme (s)
g = acceleration due to gravity = 9.81m/s
2
C = coefficient of spreading = 2.0
V
net
= net volumetric flowrate into the pool (m
3
/s)
This equation in its original form did not account for the contribution of heat transfer
from the ground and the flame. It was therefore modified to include the effect of enhanced
vaporization due to heat transferred from the ground and the flame. Let V
land
be the volumetric
flowrate of material out of the pool due to vaporization from ground heat transfer and V
rad
be
the volumetric flowrate of material out of the pool due to vaporization from flame heat transfer.
If V be the volumetric flowrate of material into the pool, the net flowrate into the pool will be
given by the following equation:
If we assume the ground to be a semiinfinite medium, the volumetric flowrate due to
vaporization arising from ground heat transfer can be expressed as:
51
If the pool ignites and we assume that a fraction of the radiation from the flame is
redirected into the pool, the volumetric flowrate of out of the pool can be expressed as:
The emissivity of luminous flames is discussed later. It is also shown that emissivity depends
on the path length. For radiation that is redirected to the pool, the path length is a function of
pool diameter. Hence the emissivity is a function of pool diameter. Combining the above
equations yields a differential equation which can be solved to obtain the variation of radius
with time.
3.2.3 Unconfined Instantaneous Releases
For unconfined instantaneous releases, the model suggested by Raj and Kalelkar18
is used. Raj and Kalelkar developed an expression for spreading and burning of an
instantaneous release of liquid. This expression was obtained by equating the gravitational
spreading force to the inertial resistance and accounting for the loss of mass continuously
during the process. The radius of the pool increased with time until all the fuel was consumed
by the fire. The maximum diameter of the pool and the time at which this occurred were given
by the following equations:
52
3.2.4 Thermal Radiation
The thermal radiation intensity at any point is calculated as before. The maximum
emissive power, liquid burning rate, flame emissivity, maximum view factor, and atmospheric
transmissivity are calculated just as in the confined pool fire model.
3.3 Jet Flame Model Theory
The jet flame radiation model predicts the visible length, the approximate diameter
and the liftoff distance of vertical gaseous jet flames resulting from high pressure pipeline
accidents in which the escaping flammable gas is ignited. It also calculates thermal radiation
flux levels at up to ten userspecified distances, at target heights that are preselected
fractions of the maximum jet flame extent. The calculation procedure is described in the
following sections.
3.3.1 Jet Flame Length
The selected model assumed that the jet flame shape is cylindrical. It model also
assumed that the gas obeyed the ideal gas law and that the flow was isentropic. A gas of
molecular weight, Mn was assumed to be flowing from a reservoir at pressure Pn and
temperature Tn through a hole of diameter d, with an effective discharge coefficient, Cd , to
another reservoir at pressure Pa and temperature Ta. For a total pipe rupture, the diameter of
the pipe was used. For simulating field accidents, a rectangular shape was assumed with a
and b being the short and long dimensions of the opening. In this case, the equivalent
diameter of the hole was estimated from:
53
54
55
56
3.3.2 Thermal Radiation
The thermal radiation intensity at any given point is calculated as before. The
maximum view factor and atmospheric transmissivity are calculated using the same equations
used to calculated thermal radiation flux from confined pool fires.
The maximum surface emissive power for jet fires is set in the Chemical Property Database
for the material. If a value for the surface emissive power for a jet fire for the material is not
entered in the Chemical Property Database, the emissive power for the jet fire is taken as
twice the maximum surface emissive power for pool fires.
As a result of good mixing within the flame because of turbulence, the surface
emissive power is likely to be higher that that seen in pool fires. Since known values of the
surface emissive power for a material tend to be based on pool fire experiments, it is
reasonable to use a value for the emissive power for a jet flame which is twice this value.
57
3.4 BLEVE Model Theory
58
4 (Explosion Modeling)
4.1 TNT Equivalency Explosion Model Theory
TNT Equivalency Explosion models express the potential explosive power of a vapor
cloud as a single, equivalent TNT charge located in the clouds center.
The Equivalent charge weight of TNT,
Using the Hopkinsonscaled distance, the sideon peak overpressure can be read
from the appropriate chart of experimental results. The HSE methodology uses blast data
from Marshall V.C. . The US army model uses blast data from the U.S. Army.
4.2 TNO MultiEnergy Explosion Model Theory
This model is based on the work of TNO. It takes into account the variability of the
blast strength by expressing the explosion as a number of fuelair charges each with
individual characteristics. Hence, the vapor cloud explosion is modeled as a number of
smaller blasts, each centered on a confined section of the cloud.
For each confined blast source:
The Energy of Explosion (J), E = M
f
H
f
where: M
f
= Mass of fuel in the confined part of the cloud (kg)
H
f
= Heat of combustion (J/kg).
59
4.3 Baker Strehlow Explosion Model Theory
This model is based on the work of Baker and Strehlow. It takes into account the
variability of the blast strength by expressing the explosion as a number of fuelair charges
each with individual characteristics. Hence, the vapor cloud explosion is modeled as a
number of smaller blasts, each centered on a confined section of the cloud.
For each confined source of ignition:
The Energy of Explosion (J), E = M
f
H
f
G
where: M
f
= Mass of fuel in the confined part of the cloud (kg)
H
f
= Heat of combustion (J/kg)
G = Ground Reflection Factor.
60

61
References
References for Dispersion Modeling
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PLTR912119, ADA246726, 1991.
2. Spicer, T. and Havens, J. EPAs Users Guide for the DEGADIS 2.1 Dense Gas Dispersion
Model. EPA450/489019
3. Spicer, T., Havens, J., Tebeau, P. Key, L. DEGADIS A HeavierThanAir Gas Atmospheric
Dispersion Model. Paper Presented at the 79th Meeting of the Air Pollution Control
Association, Minneapolis, MN. June 2227, 1986.
4. Ooms, G.A., Mahieu A.P., and Zelis, F. The Plume Path of Vented Gases Heavier than Air,
First Symposium on Loss Prevention and Safety Promotion in the Process Industries. Elsevier
Press, 1974.
5. Ermak, D.L. Users Manual for SLAB: An Atmospheric Dispersion Model for DenserThan
Air Releases. DE91008 443, 1990.
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Wind and Diffusivity Profiles. Atmos. Environ., 9:175189, 1975.
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Surface Fluxes from Routine Weather Data. J. Climate Appl. Meteorol., 22:517529, 1983.
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Sensible and Latent Heat During Daytime Compared with the PenmanMonteith Concept. J.
Appl. Meteorol., 21:16101621, 1982.
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