A Model of Dilution of Vapor- Liquid Chemical Plume in

Horizontal Wind.

CHAPTER 1

1
 INTRODUCTION

An accidental release of liquid or gaseous fuel indoors or to the outside

is a safety problem that is frequently considered by the chemical and waste
remediation industries that process and/or store flammable substances. The
release almost always occurs in the form of a negatively or positively
buoyant, continuous jet which mixes with the ambient air. All possible
fuel/ambient air mixture compositions occur within the buoyant jet between
its source and the far field of the jet. There are many cases m the chemical
industry where various chemicals are stored under pressure, and at
temperatures exceeding their normal boiling point In the case of an
accidental release under such conditions, the material emerges from the
release point (e.g., orifice, rupture, etc.) as a liquid that immediately flashes
to form a two-phase jet.

After the extremely serious accidents which happened in the chemical,

petrochemical and petroleum industry in the last 3 decades, the safety
authorities have to reconsider the procedures and the models dedicated to
the assessment of potential hazards. In particular, one may have to
determine the impact on the environment of an accidental release of toxic or
flammable chemicals. Many releases to be considered involve high-
momentum two-phase discharges. This may occur from emergency venting
of vessels due to fire exposure or runaway reaction, or from accidental
breaches in vessels, pipes or sealing. In the case of storage of pressurized
liquefied gas, venting induces flashing of the superheated liquid; in the case
of thermal runaway reactions, gassy reaction products can be released with
the liquid phase. Releases involving two-phase flow exhibit specific
characteristics which can significantly influence the dispersion process. The
rather recent realization of the importance of these effects has led to the

2
development of two-phase dispersion models. A comparative review of these
models is proposed here. To clarify
the situation under study and to introduce basic definitions, a description of
the phenomena taking place in the dispersion process is first recalled.[ P.
Bricard et al., 1998]

Mathematical modeling of the dispersion of the vapors resulting from accidental releases of
volatile liquids and heavy gases has been helpful in establishing safe designs and operating
procedures for the transport and storage of flammable and toxic materials.

Increased recognition that most emergency release from chemical storage or process vessels
involve the escape of volatile, pressurized liquids has led to a need for predictive models of two-
phase liquid-vapor forced plumes (jets). In many postulated releases from chemical and process
plants, the material contained within the plant is ejected through a break as a two-phase jet or
cloud which then disperses into the surrounding atmosphere. The growing realization that most
emergency releases involve high momentum two-phase discharges even in cases of controlled
releases, has led to increased interest in modeling such jet releases. Releases of liquids from
pressurized vessels have high momentum. A rapid depressurization and expansion occurs just
outside the release orifice. During depressurization the liquid jet material is converted into
aerosol as a result of flashing to vapor. Following external expansion to atmospheric pressure,
turbulent mixing of the jet with the atmosphere occurs and the surrounding air and water vapor
are entrained into the jet at a rate proportional to the mean jet velocity. [M. Epstein et al.,1990]

The temperature of the jet decreases with distance from the release point, owing to the
evaporation of the jet aerosol by the entrained, relatively warm air. As a result the water vapor in
the entrained air may condense to a fog. The observed persistence of visible aerosol plumes
produced by the release of volatile liquids is probably due to condensation of the atmospheric
water content. Beyond some not very significant distance from the release point (source) both
liquid phases, jet material and water, are consumed by evaporation and the forced plume
behavior is one of an all-gas heavier-than-air release. As dilution continues and the jet slows
down, it begins to spread over the ground under the influence of gravity and loses its roughly

3
circular shape. As demonstrated later, in this intermediate jet slumping (or gravity current) phase
the rate of entrainment of air is still proportional to the mean jet flow velocity, with the
proportionality factor taken to be a constant. In the final phase of jet behavior, far from the
release point, the atmosphere eddies determine jet dilution behavior.

A theory for the spreading of a steady-state initially high-momentum two-phase jet in a

horizontal wind is proposed here, in which it is assumed that for some rather large distance
downwind of the release location (in some cases of the order of thousands of meters), the effects
of buoyancy and/or atmospheric turbulence on the inflow or entrainment velocity may be
ignored in comparison with the effects of turbulence generated by the jet. This assumption is
what distinguishes the present work from most of the previous modeling efforts, which are based
on the notion that the rate of engulfment of air by the jet is determined by the atmospheric
boundary layer and/or by gravity beginning at relatively small distances from the source. In the
present model only two distinct phases of jet entrainment behavior are considered: mixing by the
jet’s self-generated turbulence in the near field and mixing by environmental turbulence in the
far field. Moreover a fairly sharp transition point at which near-field entrainment behavior
changes to far-field behavior is assumed. The intermediate phase involving the inhibiting effect
of buoyancy on mixing into the jet is regarded as insignificant.

1.1 Factors affecting two-phase toxic releases

The main factors affecting the consequences of a two-phase release are:

1) The scale and duration of the release, and the rate at which material becomes airborne,
i.e. the source term

2) The rate at which the material disperses in the atmosphere and the direction of the wind,
i.e. dispersion;

3) The toxicity of the material;

4) The population distribution surrounding the hazardous plant and their response to the
emergency. . [Fauske et al.,1988]

4
 .

Fig 1.1: The path of a two-phase release into the atmosphere.

1.2 The three regions of two-phase jet dispersion model

1.2.1 Depressurization Zone

Here aerosol formation takes place. In this region the jet undergoes a rapid
depressurization to or slightly below ambient pressure within a distance from the release
orifice of approximately two orifice diameters. It is within this zone that the liquid
disintegrates into fine droplets in the lo-50pm size range. The jet expansion in this region
is rapid and due almost entirely to vapor production; its interaction with the atmosphere is
negligible and very little mixing between jet and ambient occurs. The depressurization
zone is treated with a standard liquid flash and momentum balance equation, as discussed
by Fauske and Epstein. The trajectory and dilution of the jet in the intermediate, elevated
jet zone is predicted with a two-phase version of the buoyant jet entrainment models that
were originally developed for smoke stack or cooling water discharge plumes

1.2.2) Jet trajectory zone:

This is two dimensional zones for above ground level releases. This zone begins
when the jet is depressurized to atmospheric pressure. The forced plume (jet) is not
necessarily released at ground level and the component of initial jet velocity, u,, is not
necessarily parallel to the horizontal ambient flow (wind), but may be inclined away from
it, horizontally. Thus near the rupture opening (or vent) the solution of the equations of
motion may require that the jet rise. However, further downstream the heavier-than-air jet

5
 is influenced by the gravitational field and its trajectory is similar in shape to that of a
projectile (see Fig. 1.2). The trajectory ‘zone’ or, equivalently, the flight of the jet
terminates upon contact with the ground.

1.2.3) Ground level dispersion zone:

This is region beyond the distance to plume ‘touchdown’. This region begins at
touchdown or, in mathematical terms, when the elevation of the centerline of the jet is
equal to its radius (i.e. z = R, see Figure 1.2). The atmospheric dispersion of the ground-
level jet is affected by both entrainment of the atmosphere and gravity spreading. Gravity
spreading is driven primarily by the excess hydrostatic pressure caused by the density
difference between the jet and the atmosphere[ M. Epstein et al., 1990].

Choked, liquid or two-phase jets are characterized by a rapid depressurization to or slightly

below ambient pressure within approximately two break diameters from the outlet and very little
mixing between jet and ambient over this distance. Downstream of the depressurization zone, the
pressure within the jet may be taken to be constant and equal to the ambient pressure, and the
flow within the jet is strongly influenced by an intensive exchange of mass with the atmosphere.8

A flashing release is defined as a release of superheated liquid above a critical temperature that
results in shattering of the liquid due to vapor expansion (thermal shattering). It is the liquid
breakup and bubble bursting at surfaces that create respirable droplets. This can be for either
stagnant pools (e.g. a vessel) with sudden depressurization or a jet from a pressurized leak.

If a leak in a vessel or line occurs above the vapor space, the release will be in the form of a gas.
The gas will often be under pressure, so that the release will take the form of a high velocity jet.
As the gas exits the orifice and makes the transition to atmospheric pressure, there will be a
sudden expansion of the jet cross-section perpendicular to the direction of flow. The jet then
begins to decelerate as ambient air is entrained. The concentration within the jet is inversely
proportional to the radius of the jet, rather than its cross-sectional area, as would be the case for a
passive plume. In its early stages, the jet trajectory is virtually a straight line whose elevation and
azimuth angles depend upon the location of the leak or the orientation of a safety discharge

6
valve. Since safety valves or rupture disks can be designed to direct jets upward, the
consequence of the release is far less serious than would be the case if the storage vessel itself
ruptured, giving rise to a liquid release near ground level. After a sufficient amount of air is
entrained, the jet release will be carried along with the ambient wind. If, however, the release is
significantly heavier than air, the jet could fall to the ground before this passive state is reached.
[Woodward J.L.,1989]

Fig. 1.2: Flow regimes of a high-momentum two phase release and coordinate system.
[ M. Epstein et al., 1990]

7
Fig. 1.3: Idealized cloud section: side and cross-sectional views of a two-phase, elevated
continuous release at various stages of dispersion [Brown R. et al., 1962].

1.3 Chemical plume

Fig. 1.4: A chemical plume emitted from finite source decreases in concentration as
chemical carried away from the source and dispersed by air and different
concentration levels.

In the case of two-phase toxic releases, the source terms of prime interest to HSE arise from loss
of containment accidents in plant processing or storing superheated (i.e. pressurized so that the

8
liquid is above its boiling point at atmospheric pressure) liquefied gases. The transfer processes
associated with the subsequent discharge of material to the atmosphere are complex, and involve
non-equilibrium two-phase ‘flashing’ flow. rapid expansion of the jet and further flashing of
liquid as the jet emerges from the breach, break-up of the liquid into droplets and aerosol with
possible liquid ‘rain-out’, and entrainment of air into the jet as it expands. Air entrainment
rapidly lowers the partial pressure of the vapor, thus causing further evaporation of the liquid
droplets, with much of the latent heat of vaporization coming from the sensible heat in the air as
it is cooled to the liquid droplet temperature although some will be taken from the liquid also).
These processes have been described comprehensively [Fauske et al.,1988].

1.4 Dispersion Process

The release is supposed to originate from a relatively small hole so that continuous, i.e.
quasi-steady, conditions at the outlet can be assumed. The cloud is defined as the smallest
control volume containing the contaminant. In its first stage, where its initial momentum
dominates, the cloud will also be referred to as jet. In most cases involving two-phase releases,
the flow is choked at the exit and an external depressurization zone, where the pressure decreases
down to the atmospheric pressure, is formed. When the exiting liquid is sufficiently superheated
with
respect to ambient conditions, it is atomized by violent vaporization .Otherwise, the liquid or
two-phase mixture is disintegrated due to liquid surface instabilities aerodynamic atomization..
Downstream from this region, air entrainment at the perimeter of the cloud becomes important,
which causes it to further widen .At least for some distance; the cloud may be dense, i.e. heavier
than air, as a result of high molecular weight(e.g. chlorine).or low temperature and airborne
droplets (e.g. evaporating ammonia).

The dispersion of the contaminant in the atmosphere can be described in terms of cloud
trajectory and dilution. From an integral point of view, the trajectory is given by a momentum
balance on the cloud; the main effects involved are cross-wind, gravity and friction on the
ground after touchdown. The dilution is controlled by the rate of air entrained in the cloud. Near
the outlet, this is governed by the turbulence generated by the jet itself; it is then controlled by
atmospheric turbulence when the jet velocity has decreased close to that of the ambient wind.

9
The dilution is controlled by the rate of air entrained in the cloud. Near the outlet, this is
governed by the turbulence generated by the jet itself; it is then controlled by atmospheric
turbulence when the jet velocity has decreased close to that of the ambient wind. Moreover, the
interaction with a cross-wind induces an enhancement of the entrainment rate. In the case of
dense clouds, gravity may also have an effect on air entrainment, related to gravity-induced
turbulence as well as suppression of atmospheric turbulence due to stable stratification. In the
following, the region of passive dispersion due to atmospheric turbulence only is referred to as
the far-field and the upstream region as the near-field.

The dispersion process may be significantly affected by the presence of an aerosol phase. First,
two-phase releases can lead to much higher discharge mass flow rates than single-phase gas
releases and, thus, increase the hazard zone distance. Moreover, the jet density may be
significantly higher. It can firstly be increased by the mere presence of the liquid phase.
However, this is only significant very close to the outlet, where the liquid mass fraction averaged
over the jet cross-section is not negligibly small. The aerosol effect on jet density is mainly due
to phase change phenomena. When the liquid contaminant evaporates, the jet may significantly
cool down and, thus, increase in density. A gas which has a smaller molecular weight than air
like ammonia can then behave as a heavy gas. The cooling process may also lead to the
condensation of the entrained humidity. If the contaminant is hygroscopic, this can lead to its
persistence to significantly larger distances from the outlet. The formation of the aqueous aerosol
will cause the mixture to warm up more rapidly and have less density. Furthermore, a part of the
liquid may not remain airborne in the jet and fall to the ground where an evaporating pool could
build up; such a pool may also be formed from the jet impingement on a surface. This so-called
rainout could induce a drastic reduction of the downstream contaminant concentration but
increases the danger close to the source as well as the duration of the dispersion [P. Bricard et
al., 1998].

CHAPTER 2
TWO PHASE CHEMICAL PLUME MODEL

10
 The dispersion models which take into account the presence of an aerosol phase have
appeared only recently literatures. They are either integral or multi-dimensional models. Integral
models are obtained by integrating the balance equations for mass, momentum, energy and
species over the cloud cross-section. Integral models are obtained by integrating the balance
equations for mass, momentum, energy and species over the cloud cross-section.

A schematic representation of the high-momentum two-phase plume is shown in Figure 2.1 The
jet is inclined and released above ground level. The jet passes through several physical regimes
along its path. The regimes are modeled separately in the following sections.

Fig. 2.1: Two Phase Jet Release[Bricard P.,1998].

2.1 Depressurization zone

The jet expansion in this region is rapid and due almost entirely to vapor production; its
interaction with the atmosphere is negligible and very little mixing between jet and ambient
occurs. Thus friction, heat and momentum exchange with the ambient environment at pressure P,
are assumed to be negligible.

In an emergency release situation, liquid at high pressure usually escapes from a vessel whose
stagnation condition is sub cooled and exit choked mass flux well-represented by,

11
 G= CD2P0-Pj,s(T0)ρj,f (1)

where PO is the stagnation pressure; Pj,s(To) is the vapor (or saturation) pressure of the escaping
jet material corresponding to the liquid stagnation temperature T0; and ρj,f is the density of the jet
material’s liquid phase. This Bernoulli type expression shows reasonable agreement in
experimental comparisons. Equation (1) is derived below:

let, P1= P0 ;
P2= Pj,s(T0)

form of Bernoulli’s equation,

P1+u12ρ2=u22ρ2+P2

P1-P2=u22ρ2 As u1 =0;

P1-P2=u22ρ22

We know,
G2=Kgm2sec: and also , u2×ρ2= Kgm2sec

We can write, u2×ρ2= G;

P1-P2=G22ρ

G2=2ρP1-P2

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 G=2ρP1-P2

G=CD2ρP1-P2

Thus equation (1) is derived,

A space wise calculation of two-dimensional (or ax symmetric) jet pressure and velocity profiles
is difficult. However, it is possible to estimate the fully expanded jet properties at the end of the
depressurization zone, when the jet pressure everywhere has approached the ambient pressure.
High pressure flashing liquids produce extremely fine droplets, so that phase velocities and
temperatures are quickly equalized. The principle of conservation of momentum flux applied to
this homogeneous mixture provides a simple relation between the fully expanded jet velocity u,
at\ the end of the depressurization zone and the break (or choke) plane quantities:

ue=Gρj,f+Pj,sT0-P∞G (2)

To obtain the quality of the fully expanded jet, x,, we invoke the condition of constant
stagnation enthalpy.
ho =hj,f,sP∞+xehj,f,g(P∞) (3)

The kinetic energy of the two-phase jet is notably quite low (relative to that of an all-gas sonic
discharge) and therefore is not included in the above equation. For the all-liquid discharge
considered here, Equation (3) becomes,

xc= cj,f[T0-Tj,sP∞hj,fg (4)

The area of the depressurized jet A, is related to the area of the break Ab through the equation for
the conservation of mass,

13
 Aa=Abubρbuaρa=AbGucρc

in which the expanded jet density, ρe, is given by the definition,

ρe=xeρj,g,sP∞+1-xeρj,f,sP∞-1

(5)

The volume occupied by the liquid at the end of the depressurization zone can readily be shown
to be negligible. Thus the equilibrium quantity ρj,g,sP∞ can be identified with the mass of the
vapor per unit spatial volume, i.e.

ρj,g,e=ρj,g,sP∞ (6)

The mass of the liquid phase with respect to the same spatial volume is given by

ρj,g,e=1-xeρc (7)

The quantities ue,Ae,ρj,g,e and ρj,f.e are used as input to the jet trajectory and dilution model.

[ M. Epstein et al., 1990]

2.2 Air born jet trajectory zone

This zone begins when the jet is depressurized to atmospheric pressure. The forced plume
(jet) is not necessarily released at ground level and the component of initial jet velocity, ue is not
necessarily parallel to the horizontal ambient flow (wind), but may be inclined away from it,
horizontally. Thus near the rupture opening (or vent) the solution of the equations of motion may
require that the jet rise. However, further downstream the heavier-than-air jet is influenced by the

14
gravitational field and its trajectory is similar in shape to that of a projectile. The trajectory
‘zone’ or, equivalently, the flight of the jet terminates upon contact with the ground.

The equations are written to take account of a steady, horizontal, wind. The wind direction or,
velocity, ‘W’ does not change with altitude z, the jet lying in the x, z plane (see Figure 1.2). The
mean velocity inside the jet is denoted by the symbol u. The centerline of the jet makes an angle
θ with the horizontal, ‘s’ is the distance along the jet, ‘A’ is the cross-sectional area of the jet,
and ‘C’ is the perimeter of the cross-section. For simplicity, we assume that inside the jet the
velocity, vapor and liquid concentrations, and temperature are uniform in the crosswind plane.
Over the distance the jet is airborne its cross-section is taken to be circular and its radius ‘R’ is
assumed to be small compared with the centerline radius of curvature (slender plume
approximation).

Once the jet is depressurized to atmospheric pressure, the jet expands solely by entrainment of
ambient air. The principal assumption of this theory is that, for some significant distance from
the source, the effects of atmospheric turbulence may be ignored, provided the initial momentum
of the jet is high enough. Some performed an analysis on a limited set of experimental data on
buoyant jet flow discharged into a uniform cross stream to determine the jet entrainment velocity
due to the jet’s self-generated turbulence. For jets with a two dimensional trajectory, then
expression becomes,

ven=ρρ∞1/2E0u-Wcosθ+E1Wsinθ
(8)

Where the term u-Wcosθ represents the relative velocity of the jet with respect to the wind.
Actually, Equation (8) is a combination of the entrainment model proposed by Hirst and the
entrainment model of Ricou and Spalding for vastly different jet and ambient densities, p and
pm, respectively. Precise definitions of ρ and ρ∞ are given below. Equation (8) reduces to the
entrainment function of Hirst in the limit ρ ρ∞ .The constants of proportionality Es and Et are
called the entrainment coefficients. Some authors have verified through measurements that for
pure momentum jets (E1 = 0) values of E0 lie within the range 0.06 to 0.12.

15
If a uniform velocity profile is used E0 = 0.12 results in the best agreement between theory and
experiment. From data on buoyant water jets discharged at varying angles into flowing aqueous
salt solutions, the specified the values E0 = 0.057 and El = 0.513. In the calculations which
follow, we shall adopt Equation (8) and use values of E0 and El of 0.1 and 0.2, 0.5, respectively.
The jet trajectory can now be determined from the conservation equations for mass, momentum
and energy, using the entrainment equation to determine the rate of mass, momentum and energy
addition into the jet. [ M. Epstein et al., 1990]

The equation for the conservation of mass of the discharge material,

ddsρj,g+ρj,fuA=0 (9)

The equation for the conservation of mass of the air,

ddsρauA=ρa,∞venC (10)

The equation for the conservation of mass of the atmospheric water content,

ddsρw,g+ρw,fuA=ρw,g,∞venC (11)

Note that in addition to the liquid aerosol of the discharge jet material we allow for the
possibility of water droplet formation via condensation of the entrained water vapor within the
cold jet (see Equation (11)). Neglecting the volume occupied by the jet aerosol and water
droplets, we can express the overall spatial density, p, of the three components two-phase
Mixture as the sum of the spatial densities of the components,

ρ=ρj,g+ρj,f+ρa+ρw,g+ρw,f (12)

16
The momentum equation in the vertical direction is a balance between plume momentum and
mass,

ddsρAu2sinθ=-gρ-ρ∞A (13)

where ρ∞ is density of the air/water vapor atmosphere, namely

ρ∞=ρa,∞+ρw,g,∞ (14)

The momentum equation in the horizontal direction is a balance between jet momentum and
momentum entrained,

ddsρAu2cosθ=WddsρAu (15)

Conservation of heat may be written in the following form,

ddsρuAh=ρa,∞venCha,∞+ρw,g,∞venChw,g,∞
(16)

where h is the overall enthalpy of the mixture within the jet; it is given by the definition

ρh=ρj,ghj,g+ρj,fhj,f+ρaha+ρw,ghw,g+ρw,fhw,f (17)

The energy equation, Equation (16), may be readily converted from enthalpy to temperature as
the dependent variable by introducing the thermodynamic relation h(T) for each species,
assuming the vapor phases are ideal and the liquid phases are incompressible. The height z of the
jet above ground level is, in differential form,

dz ds=sinθ (18)

and the horizontal distance ‘x’ from the rupture opening is given by,

17
dxds=cosθ (19)

Note that in writing the above equations, we have neglected the length of the depressurization
zone. This length is typically quite small relative to the range of the jet. To predict the densities
of the vapor phases in the presence of their condensed phases it is assumed that thermodynamic
equilibrium is locally achieved within the jet. Thus, utilizing the ideal gas equation of state, we
have,
Ideal gas law is,
PV=nRT
From this we get,
ρj,g=Pj,sTRjT (20)

ρw,g=Pw,s(T)RwT
(21)

The pressure within the jet is equal to the atmospheric pressure P∞. This requirement gives,

P∞=ρj,gRjT+ρw,gRwT+ρaRaT (22)
Finally, since the cross-section of the jet is taken to be circular, the radius R, circumference and
cross sectional area are related by the expressions,

C=2πR=2(πA)1/2 (23)

2.3 Boundary conditions

The above equations express the mathematical formulation of the model and are sufficient to
determine the nine coupled unknown quantities, ρj,g , ρw,f,ρa,u ,A ,T and θ as a function of
the
Coordinates x, z. These quantities are subject to the following initial conditions when x = 0 and

18
z = z0,

ρj,g=ρj,g,e ,ρj,f=ρj,f,e (24)

ρw,g=ρw,f=ρa=0 (25)

u=ue , A=Ae (26)

T=Tj,s ,θ=θ0 (27)

The initial thermodynamic state of the mixture, at the end of the depressurization zone, is one of
jet material aerosol in equilibrium with its vapor phase. Downwind of the release point humid air
is entrained into the jet causing further evaporation of the liquid jet material. At first water exists
within the jet only as vapor and Equation (11) is integrated with ρw,f=0 . [ M. Epstein et al.,
1990]

As a result of a combination of the cooling of the jet by the evaporation of the released liquid jet
material and the buildup in the water vapor concentration by entrainment of the surrounding air,
the water vapor may become saturated so that both vapor and liquid water are present in the
system. In some systems there is a tendency of jet material vapor to be soluble in liquid water.
This effect is ignored in the present model. As the amount of air increases, the liquid water also
begins to evaporate. Ultimately all the water and all the jet material are in vapor form. Usually
the water is the last to evaporate. The evaporation of the water in the far field will tend to
prolong the persistence of the cool jet beyond the distance to ground contact.

2.4 Ground- level dispersion zone

This region begins at touchdown or, in mathematical terms, when the elevation of the
centerline of the jet is equal to its radius (i.e. z = R, see Figure 1.2). The atmospheric dispersion
of the ground-level jet is affected by both entrainment of the atmosphere and gravity spreading.

19
Gravity spreading is driven primarily by the excess hydrostatic pressure caused by the density
difference between the jet and the atmosphere.

In the initial phase of ground-level jet behavior, the turbulent motion within the jet is normally
still due to the movement of the jet itself and, accordingly, Equation (8) for ven remains valid.
Of course in the final phase of jet behavior, far downwind of the source, the energy containing
eddies of environmental turbulence dominate mixing and the ground-level jet growth is strictly
due to the action of the wind. The far-field jet growth is assumed to be well-described by the
Gaussian plume, point source solution to the atmospheric advection-diffusion equation.
Accordingly,\ a realistic equation for the entrainment velocity in the far field is,

ven= πWCddxσyxσz(x) (28)

Which when combined with the conservation of mass equation gives the point source Gaussian
solution for the ground-level concentration of the released species in the far field of the jet. In the
above equation, σyx andσz(x) are the dispersion coefficients (or standard deviations) for the
crosswind plane. The most widely used σy and σz functions are the so-called Pasquill- Gifford
curves. These empirically determined functions depend on the atmospheric stability classes. The
field observations reported by Burgess et al. suggest that the dispersion of heavier-than-air
ground-hugging vapors is best represented by Gaussian theory when σy and σz are based on the
most stable atmospheric condition, stability class F, regardless of the actual state of the
atmosphere. This recommendation is followed here.

Close to the source, the entrainment velocity given by Equation (8) greatly exceeds that given by
Equation (28) and vice versa at distances far from the source. One would expect, therefore, a
fairly definite transition point (or perhaps a short transition zone) at which the character of the jet
changes when the near- and far-field entrainment velocities are comparable. Therefore, during
the course of a calculation a switch is made from Equation (8) to Equation (28) at the location in
which both equations predict the same entrainment velocity, thereby merging the high-
momentum jet theory with the Gaussian plume model(A computer model used to calculate air
pollution concentrations. The model assumes that a pollutant plume is carried downwind from its
emission source by a mean wind and that concentrations in the plume can be approximated by

20
assuming that the highest concentrations occur on the horizontal and vertical midlines of the
plume, with the distribution about these mid-lines characterized by Gaussian- or bell-shaped
concentration profiles). [Nikmo J. et al., 1994]

It is obvious that by equating the two entrainment velocity laws, Equations (8) and (28), the
intermediate phase of jet behavior involving buoyancy-dominated dispersion effects has been
assumed to be insignificant. This assumption implies the dominancy of inertial force over the
buoyancy force. The ratio of jet buoyancy to inertia is given by the Richardson number, defined
by,

Ri=2g(ρ-ρ∞)zρu2
(29)

The work of Ellison and Turner showed that the entrainment is not buoyancy dominated if
Ri≤0.1 As we shall see later on, this criterion is indeed satisfied for volatile liquid chemical
releases of practical interest. It is worth noting that observations of smoke plumes from a large
power station suggest the sudden transition assumed here, from jet momentum drive entrainment
to wind dispersion.

In the present model, the ground-level dispersion is handled in the same way as the elevated
dispersion, except that the momentum equations, Equations (13) and (15), and kinematic
equations, Equations (18) and (19), are replaced by corresponding equations that account for
gravity compaction and sideways spreading. Assume that the cross-section of the ground-level
jet is rectangular, with height 22 and radius (half-width) R. Note that z still represents the
Vertical distance from the ground to the centerline of the jet. Beyond ground contact, Equation
(23) for the perimeter of the jet is replaced by the expression,

C=4z+A/(2z) (30)

This relation for the rectangular jet is derived by not allowing entrainment to occur at the jet-
ground interface. The half-width of the jet R at ground contact is calculated by setting the
perimeter and area of the rectangular ground-level jet equal to those of the circular elevated jet.

21
This ensures that in the post ground contact region the masses within the jet are conserved and
that the continuity and smoothness of concentrations- and temperature-with-distance are
preserved. A discontinuity in R will exist at ground contact.[ Heinrich M. et al.,1988]

The momentum equation applied to the side edges of the jet is,

ddsρAuv=g(ρ-ρ∞) (31)

Where u is the velocity of the jet in the lateral direction (or the spreading rate). The momentum
equation in the axial direction is,

ddsρAu2=WddsρAu-gdds[ρ-ρ∞Az] (32)

After jet touchdown, these equations are substituted for Equations (13) and (15). The motion of
the material interface represented by a side edge of the jet is given by the kinematic condition,

udRds=ven+v
(33)

where ven and v are the velocities normal to the edge. With the aid of the equation for the cross-
sectional area of the plume, namely ‘A = 4zR’, Equation (33) can be written as follows,

dzds=zAdAds-4z2Aven+vu
(34)

which replaces Equation (18) after plume touchdown. Finally, during the gravity spread
calculation, Equation (19) takes the form,

dx ds=1 (35)

22
( i.e. θ = 0 )

It should be mentioned that the only new variable that appears after the transition is made from
the airborne plume to the ground-level dispersion is the spreading velocity ‘v’; it is assigned the
initial condition v = 0 at the location of ground contact.

From this system of equations we can compute the jet temperature, released species and
entrained water concentrations, jet boundaries, jet velocity, etc. as a function of distance from the
source. To utilize available computer subroutines, the equations were converted to an equivalent
coupled system of first order ordinary differential equations by expanding the derivatives in
Equations (9)-(11), (13), (15), (16), (31), and (32).

2.5 Integral Models

Integral models can either deal with both the near-field and far-field or consider the near-
field only. In the latter case, they are regarded as source term for a far-field dispersion model.
The models are all based on the balance equations for mass, momentum, energy and species,
integrated over the jet cross-section; they mainly differ by the adopted closure relations. A
common frame based on the mixture balance equations is first proposed to enable a comparison
between the models. Then, the closure relations, or sub models, are described.[Bricard P. et
al.,1998]

2.5.1 Balance Equations

In the following, we assume that the cloud (or jet) centre-line remains in the wind–
gravity plane. Let s be the curvilinear coordinate of the cloud centre line, (x, y, z) its Cartesian
coordinates such that wind and gravity are oriented along the x and z directions, respectively
(Fig.4) and ‘θ’ the angle between the jet centre-line and the horizontal axis such that,

dxds=cosθ

23
 dzds=sinθ

With ‘A’ being the cloud cross-section area, ρ, u and h the mixture density, velocity and
specific enthalpy, respectively, and c the contaminant mass concentration (in kg/m3) in the cloud,
the balance equations for continuous (steady-state) release can then be written as,

Mixture mass balance is ,

ddsAρudA=E (36)

Contaminant mass balance is,

ddsAcudA=0 (37)

Mixture enthalpy balance is,

ddsAρuhdA=Eha (38)

Mixture x- momentum balance is,

ddsAρu2cosθdA=Eua+Fx (39)

Mixture y- momentum balance is,

ddsAρu2sinθ=Fz (40)

Where ‘E’ is the so-called entrainment function representing the rate of air entering the cloud;
ua and ha are the velocity and the specific enthalpy of ambient air, respectively. Fx and Fy are the
forces which act on jet in horizontal and vertical directions respectively [Bricard et al.,1998].

24
2.6 Forces on the cloud
Models which do not include wind and gravity effects on the jet trajectory assume
constant jet momentum so that Fx = Fy=0. Other models contain a gravity term as a contribution
of Fz .Most authors also introduce an additional drag force FD due to cross wind. This force is
supposed to be act in the direction perpendicular to cloud axis. Its component in x and y
directions are given as;

For ‘x’- direction,

FDx=CDC(0.5)ρa(uasinθ)2sinθ

For ‘y’ direction,

FDz=CDC(0.5)ρa(uasinθ)2cosθ

where CD is a drag coefficient. A constant value of 0.3 is adopted mostly. The addition of a drag
force may be useful to take into account the pressure gradient perpendicular to the jet flow;
however, the drag coefficient should be drastically lower than for the flow around a solid
cylinder due to suction effects [ Bricard P. et al.,1998].

25
 CHAPTER 3

SOME TWO PHASE MULTI DIMENSIONAL MODELS

We will discuss some two phase multidimensional models that we consider subsequently
are the one of Wiirts et al., (1996), Vandroux-Koenig et al.,(1997) and Pereira and Chen (1996)

3.1 Wiirtz et al.,Model

This three-dimensional model includes the mixture mass, momentum and energy Balance
equations as well as the mass balance equation for the contaminant component. The mixture is
composed of the contaminant (liquid and/or gas) and the ambient gas (no humidity condensation
is considered. Thermo dynamical equilibrium is assumed, i.e. all the components share locally
the same temperature and pressure. The two-phase mixture is supposed to behave ideally i.e.
Raoult’s law is used for the calculation of the partial pressures. A single-phase turbulence model,
based on the eddy diffusivity concept, is adopted and modified to take into account anisotropy
effects. The working fluid is treated as a mixture of two fluids in thermodynamic equilibrium.
Both fluids may contain several components. The fluid kinetics is described by assuming a slip
velocity between the liquid phase and the ambient gas. A vertical slip velocity is allowed for
between the liquid and gas phase. Special attention was paid on the model’s ability to handle
complex terrain. In particular, liquid deposition on solid surfaces is taken into account. Remarks
already made regarding the assumption of thermodynamic equilibrium in the integral models

26
also apply here. The first validation tests performed by the authors have shown the better
performance of this model against a 1-D model when obstacles are present.

3.2 Vandroux-Koenig et al., Model

This model is devoted to the prediction of the near-field dispersion of liquefied propane.
It is a Eulerian–Eulerian two-fluid model which considers three components: propane (liquid and
vapor)., dry air and water (liquid and vapor). The condensed water is included in the gas phase to
form a homogeneous fog mixture. Balance equations are written for the mass of each constituent,
for the momentum of the gas mixture and of the propane droplets, and for the gas mixture
energy. The temperature of the propane droplets is supposed to be uniform, equal to the
saturation temperature at atmospheric pressure, so that no energy balance equation is needed for
the liquid phase. To close the system of equations, a single-phase turbulence model based on the
Prandtl’s mixing length theory is introduced for the gas phase. For interfacial transfers, a
constant droplet diameter is assumed throughout the calculation. The momentum and heat
interfacial transfer terms are calculated from a drag and a heat transfer coefficient, respectively,
for rigid spheres. The mass transfer is modeled by assuming that the heat transferred from the
gas phase to the droplets completely contributes to vapor production.

According to the authors, the propane droplets are predicted to persist much further downstream
than experimentally observed. Several possible causes were investigated for this underestimation
of droplet evaporation. Neither the assumption of a constant diameter nor the fact that no initial
radial velocity was taken into account could explain this under evaluation. On the other hand, the
assumption of a uniform temperature in the droplet or the inadequacies of the turbulence model
(the droplets may in reality disperse more than the gas phase) have been proposed as possible
explanations. More parametric studies as well as the comparison of the prediction with the
results of controlled laboratory experiments adapted to the validation of the uncertain aspects of
the model are required to solve these inconsistencies.

3.3 Pereira and Chen’s Model

This Eulerian-Lagrangian model is also devoted to the near-field dispersion of liquefied
propane; the single-phase version developed for the far-field dispersion is not considered here. It
is constituted of a Eulerian description of the mixture phase composed of air and propane vapor

27
(no humidity is taken into account) having the having the same velocity and temperature but
different volume fractions, and a Lagrangian modeling of the droplet phase which is composed
of various droplet-size groups having their own initial characteristics (velocity, temperature,
diameter,…). The effect of the dispersed phase on the gas phase is limited to the mass,
momentum and enthalpy transport due to the phase–change process. For each of the two size
classes of droplets, the equation of motion is written. The interfacial force is determined by using
a drag coefficient valid for solid spheres and with the relative velocity evaluated from the mean
local gas velocity.

The Lagrangian approach has the advantage to account for the instantaneous flow properties
encountered by the particles. A second cited advantage of the Eulerian–Lagrangian approach is
the possibility to readily handle the evolution of a distribution of particle diameters, which
remains difficult to predict in a Eulerian–Eulerian scheme. However, transient situations are
more easily solved by a Eulerian–Eulerian approach. This seems to favour the choice of
Lagrangian models for the description of the continuous releases considered here. The first
advantage is, however, not used by Pereira and Chen since only the mean local gas
characteristics are taken into account in the droplet equations.

28
 CHAPTER 4
EXPERIMENTAL DATA AND MODEL VALIDATION

The tests whose results we have used for model comparisons are: Desert Tortoise (DT) 4
liquid ammonia (NH,) release; Goldfish (GF) 1 and 3 liquid anhydrous hydrofluoric acid (HF)
release; and Energy Analysts’ (EA) 1 and 2 small-scale liquid ammonia and propane releases.
The choice of these tests is based on the availability of good experimental data. The test
parameters are shown in Table 1. Additional test details can be found in the references cited
below. It should be noted from the table that the liquids were released in the direction of the
wind approximately 1 m above ground level as a horizontal jet (θ=0). The only exception was
EA ammonia test 1 where the release angle from the horizontal θ0=100. Thus in most of the
tests the jet, made contact with the ground a short distance downwind from the source. The
release heights were not reported for the Goldfish series of tests. For the purpose of carrying out
HF dispersion calculations, a release height z0=0.79m was assumed. Ammonia was released
from this height during the Desert Tortoise series of tests, which were conducted at the same test
site as the Goldfish tests.

The Desert Tortoise series test results were reported By Goldwire et al. and Goldwire. In
Figure 5, the predicted profile for the DT4 ammonia plume is presented out to 300 m from the
source. Water droplet formation is predicted to occur essentially at the source. The jet is
predicted to impact the ground at 2.92 m downwind from the source. Goldwire et al. reported
that a noticeable pool of liquid ammonia persisted within at least 3 m of the source. The liquid
ammonia and water aerosols are predicted to evaporate completely at 40.7 and 201 m downwind,
respectively. The actual plume was visible to a point approximately 400 m downwind,
indicating, perhaps an over prediction of the entrainment rate. The calculation suggests that the
atmospheric water content is responsible for long range visibility of the plume and not the liquid
ammonia.[ Goldwire et al.,1986]

29
The temperature and ammonia concentrations versus distance from the source are compared in
Figures 4.4 and 4.5. The predicted quantities represent average values, while the experimental
data for the temperature in the far field and the concentration are the measured values close to
the centre of the jet at an elevation of 1 m. The temperature measurements in the near field, at the
3, 6, and 9 m locations, represent those of the liquid ammonia deposited on the ground just
downwind of the source. As seen in Figure 4.4, the model is in excellent agreement with the
measured temperatures in the near and far field. The model performance in the far field,
however, may not be as average temperatures while the measurements correspond to jet
centerline values at an elevation of 1 m. In Figure 5, the model is seen to predict the ammonia
concentration at the 100 m position and under predict the concentrations at the 800 and 1000 m
positions by factors of 2.0 and 3.0, respectively (see also Table 2). This level of accuracy is
considered to be reasonable in the field of modeling the dilution of chemical releases in the
atmospheres. Again, the model results are average values, while the experimental data are the
measured values at the centre of the jet.

Interestingly enough, the entrainment velocity v, given by Equation (8) did not fall below u,,
given by Equation (28) during the course of the calculation that produced the NH3 concentration
versus distance curve of Figure 5. Thus for a distance downwind of the source of at least 3000 m,
it does not appear to be necessary to invoke the presence of atmospheric turbulence due to wind
to explain the measured NH3 jet dilution. While at first sight this result may seem surprising, it
should be mentioned that many other examples have been reported in the literature in which self-
generated turbulence dominates the jet mixing process far downstream of the source.

30
TEST Ref. liquid Tj,sP∞ P0 T0 T∞ RH Ab z0 θ W
0
(K) (MPa) (K) (K) (%) (m2) (m2) ms-1

DT4 Goldwire NH3 240 1.4 297 306 21.0 0.007 0.79 0 4.5
et al.,
GF1 Blewitt HF 293 0.87 313 310 5.1 0.0014 - 0 5.6
et al.,
GF3 Blewitt HF 293 0.91 312 300 27.9 0.00046 - 0 5.4
et al.,
EA1 Pfenning NH3 240 0.83 292 292 49.0 0.00034 1.22 10 7.62
et al.,
EA2 Pfenning C3H8 231 1.03 289 289 51.0 0.000105 0.8 0 5.08
et al

Table 1: Experimental conditions for field tests

The data which show that Equation (8), with El = 0 and E0 = 0.1, can be applied to plumes
extending 3000 m above an oil fire . The distance range over which Equation (8) is valid was
extended by another order of magnitude: Wilson et al. and later on Sparks successfully applied
the formula to describe plumes of hot gas emitted from erupting volcanoes. Such plumes reach
heights greater than 40000 m. The observations of smoke plumes released from a power plant
stack into a cross-wind showed that the transition from plume-to-atmospheric generated
entrainment occurs at distances as large as 425 m from the chimney. The applied an entrainment
formula similar to Equation (8) to explain data collected on chimney plumes in a cross-wind and
found the formula to be valid over a distance of approximately 1800 m from the chimney. Note
that in such chimney plumes only buoyancy is responsible for plume momentum at the source;
yet self-generated turbulence dominates the entrainment process far downstream from the
chimney. Finally, with regard to the DT4 NH3 release simulation, it is significant to note that the

31
predicted Richardson number is 0.02 at the source, rises to a maximum value of 0.11 at about
200 m downwind and then decays to zero in the very far field. Clearly, for high-momentum jets,
gravity is not an important feature of the entrainment process.

Distance Concentration (mole Concentration (mole

fraction) fraction)
Downwind
DT4 GF3
(m)
Measure- prediction Measure- prediction

ment men
100 0.06 0.065 - -
300 - - 0.0095 0.01
800 0.02 0.0092 - -
1000 - 0.0013 0.0015
3000 0.05 0.0016 0.00018 0.00029

Table 2: Comparison of theory with concentration measurements

The hydrogen fluoride dispersion experiments were conducted and reported by Blewitt et al.
The liquid HF and atmospheric water condensate for Test GFl are predicted to evaporate in the
near field, at approximately 24 and 29 m, respectively. During GFl the jet was visible to a
distance of approximately 700 m from the source. Thus the visibility of the jet in the far field
cannot be explained by the presence of water droplets alone. Hydrogen fluoride and water vapor
exhibit a strong chemical interaction which results in the formation of a condensed phase
(aerosol) of HF/H2O solution droplets. These relatively stable, chemically produced droplets
would be expected to persist out to significant distances from the source.

The present model is based entirely on consideration of local phase-change thermodynamic

equilibrium. Chemical reactions between the jet material and water vapor are not considered.

32
The measured centerline temperatures and HF concentrations for Tests GFl and GF3 were found
to agree well with the cross-wind averaged values of the model. The measured and predicted
temperature and concentration versus distance curves for Test GF3 are shown in Figures 4.4 and
4.5, respectively. The numerical solutions indicate that the application of an entrainment
equation for high momentum jets, namely Equation (8), is not valid for distances from the source
beyond about 80 m for the HF tests. At this point the transition is made between high-momentum
jet and Gaussian plume entrainment behavior. Neglecting entrainment associated with
atmospheric turbulence will lead to over-estimates of the concentration. The predicted maximum
Richardson number for both tests is only about 0.02 at about 10 m from the source, indicating
once again that buoyancy does not influence the entrainment process in an essential way. Note
from Table I that the break area and stagnation pressure for the NH3 test are much larger than the
corresponding quantities for the HF tests. This readily explains why the NH3 jet in Test DT4 was
dominated by the momentum flux from the source at all the concentration sampler stations, while
the momentum flux for the weaker (Test GF3) HF jet vanished some distance upwind of the first
concentration sampler, and beyond this point spreading was dominated by atmospheric
turbulence. Small-scale field releases of pressurized liquid ammonia and propane were
performed by Pfenning et al. (the Energy Analysts (EA) series). Using slides and video tapes, the
average profile of the visible portion of the jet was obtained. No vapor concentration or
temperature measurements were made.

In Test EAl (see Table 1) the liquid ammonia was released at a 100 incline from the horizontal.
Figure 8 shows the predicted profile of the ammonia jet for Test EAl. The visible jet extended
approximately 45 m downwind, with a maximum height of 3.7 m. This is to be compared with
the prediction of 40.4 m, based on complete water droplet evaporation, and the predicted
maximum height of 3.9 m. The predicted length of the visible propane jet for Test EA2 is 17.9 m
and the predicted maximum jet height is 1.9 m. The visible length and maximum jet height
measured were 24 m and 2.1 m, respectively. In both the EAl and EA2 releases the jet material
aerosol is predicted to evaporate completely be ore contact with the ground. This is consistent
with the observations of that in the tests no liquid accumulated on the ground [Pfenning et
al.,1987].

33
 Figure 4.1 : Predicted jet profile for Desert Tortoise ammonia spill Test 4 (DT4)

Water fog formation At x=0.056m, height

Touchdown At x= 2.92m, height
Jet material liquid evaporated At x= 40.73m, height
Water fog evaporated At x= 201m , height

Figure 4.2: Temperature as a function of distance from source for Desert Tortoise
ammonia Test 4 (DT4).

Figure 4.3 : Ammonia concentration as a function of distance from source for Desert
Tortoise spill Test 4 (DT4)

Figure 4.4: Temperature as a function of distance from source for Goldfish hydrofluoric
acid spill Test 3 (GF3)

Figure 4.5: Hydrofluoric acid concentration as a function of distance from the source for
Goldfish hydrofluoric acid spill Test 3 (GF3).

34
Figure 4.6: Predicted jet profile for Energy Analyses ammonia release test (EAl)

CHAPTER 5
CONCLUSION

In this paper we have provided a modeling approach to determining the dispersion hazards
arising from the release of pressurized liquid chemicals. The dilution of the two-phase jet
produced by the release has been modeled taking into account the three regimes of jet behavior.
A one-dimensional source model describing the depressurization of the jet and two turbulent
entrainment models describing the elevated and ground-level behavior have been presented.

35
This review has been focused on the comparative description of two-phase jet dispersion models,
with special attention to elevated and continuous conditions. A description of available data for
two-phase jet dispersion was also given. Both integral and multidimensional models were
considered.

Most often, the integral approach has been adopted because of its good compromise between
model detail and computing timer cost, which is well adapted to hazard assessment. In integral
models, entrainment modeling remains an important issue, as reflected by the differences
between adopted formulations. Regarding two-phase flow phenomena, the homogeneous
equilibrium approximation is often used. The range where this is justified has, however, not been
defined in the case of high momentum jets. When this approximation is, at least partially relaxed,
the prediction of the initial drop size, drop trajectory and possibly evaporation is required. The
corresponding sub models show however a rather high degree of simplification and uncertainty.
Some propositions for their verification and improvement have been given. They include the
comparison of the sub models’ prediction to recent experimental data, the extension of models to
non-flashing two-phase releases and a rational criterion for droplet suspension in a jet.

Generally speaking, the models are insufficiently validated. To be able to give a firm judgment
of their quality, an independent evaluation is clearly needed. For this purpose, additional detailed
two-phase jet experiments should be performed.

36