Journal of Loss Prevention in the Process Industries 38 (2015) 39e49

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Journal of Loss Prevention in the Process Industries

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Numerical simulation of evaporation of volatile liquids

A.D. Galeev*, A.A. Salin, S.I. Ponikarov
Kazan National Research Technological University, Department of Mechanical Engineering, 68 Karl Marx Str., 420015 Kazan, Russian Federation

a r t i c l e i n f o a b s t r a c t

Article history: The paper presents the results of the validation of the developed pool evaporation model using literature
Received 21 November 2014 and our own experimental data. The proposed model was used to examine the effect of wind velocity
Received in revised form and pool sizes on the evaporation rate of volatile liquid (hexane). Contrary to the semi-empirical
27 June 2015
evaporation model widely used in hazard assessment, stronger dependence of evaporation rate on
Accepted 28 August 2015
pool size at low wind speeds is obtained.
Available online 1 September 2015
© 2015 Elsevier Ltd. All rights reserved.
Keywords:
Liquid spill
Pool evaporation
Model validation
Numerical simulation

1. Introduction effect of high vapor pressure on the mass transfer process.

The correct prediction of the consequences of hypothetical
accidental scenarios is an essential component for developing and
implementing appropriate protective capabilities and plan miti-
gation measures. This requires the use of the reliable mathematical
models describing how toxic chemicals or flammable substances
are released and dispersed in the air. A complete model for an event
can roughly be divided into three parts: source modeling, disper-
sion modeling and effect modeling (Vik and Pettersson Reif, 2011).
There is a lot of work concerning the modeling of hazardous sub-
stances dispersion in the environment, whereas little attention has
been given to source term modeling. In emergency spills of stable
liquids, the input of hazardous substances into the environment is
the result of evaporation from the pool surface.
Generally, there are two main types of mathematical models to
evaluate the evaporation rate from a pool: semi-empirical and
computational fluid dynamics (CFD) models. In the area of hazard
analysis of accidental chemical spills, many investigators and haz-
ard reference books have applied Mackay and Matsugu mass
transfer equation (Kawamura and Mackay, 1987; Mackay and
Matsugu, 1973). In the model (Kapias and Griffiths, 1999), the
mass transfer coefficient is calculated using Brighton's theory
(Brighton, 1987). This analytical model takes into account the ef-
fects of surface roughness, friction velocity of the airflow, and the
* Corresponding author.
E-mail address: galeev_ainur@mail.ru (A.D. Galeev).
Khajehnajafi and Pourdarvish (2011) used Churchill's equation
(Churchill, 1976) where the Nusselt number is determined for the
complete range of Re and Pr covering laminar, transition and tur-
bulent regimes. This equation is based on experimental data for
forced convection from isothermal flat plates. The Churchill's
equation is applied to mass transfer calculation substituting the Sh
and Sc for the Nu and Pr. The mathematical model, represented by
Habib et al. (2009), based on numerical calculation of differential
transient equations for boundary layer together with algebraic
turbulence model of Cebeci-Chang (Cebeci and Chang, 1978),
including correction for surface roughness. The above models have
been developed on the assumption that the vapor behaves as a
passive contaminant, i.e. it does not affect the flow field. This
assumption may be invalid when the molecular weight of evapo-
rating component differs from the molecular weight of environ-
ment air (Desoutter et al., 2009).
By using the CFD, it is possible to overcome the limitations of
existing semi-empirical models. This approach by solving three-
dimensional conservation equations for mass, momentum and
energy makes it possible to take into account the complex inter-
action between the evaporation process and the vapor dispersion.
Many works have used CFD to examine the evaporation rate of
water (Raimundo et al., 2014) or dilute solutions of ammonia (Rong
et al., 2010; Rong et al., 2011; Saha et al., 2011). In the work (Rong
et al., 2010) the effects of airflow and aqueous ammonia solution
temperature on ammonia transfer are investigated and the
numerical sensitivity studies are performed by Rong et al. (2011) to

http://dx.doi.org/10.1016/j.jlp.2015.08.011
0950-4230/© 2015 Elsevier Ltd. All rights reserved.
40 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49

examine the effects of computational geometry and inlet turbu- 1973; Kawamura and Mackay, 1987) it is assumed, that evaporation
lence intensity on ammonia emissions. In these studies, the rate Jg,s depends on pool size L as Jg,s ~ L0.11. The exponent on the pool
ammonia was a passive contaminant and has no impacts on airflow. dimension L was obtained by evaporating water from pools of
Raimundo et al. (2014) used CFD model to investigate the mass different sizes (Mackay and Matsugu, 1973). This exponent does not
transfer at the free surface of the water tank. In the above- reflect the buoyancy effects because the evaporation rate of water is
mentioned works, the liquideair interface is assumed to be low. The buoyancy effects are caused by the density difference
isothermal due to the small liquid volatility. When volatile liquids, between the evaporating component and ambient air and they may
such as hexane and acetone, evaporate, the liquid temperature may be significant when a pool of volatile liquid has large sizes and wind
significantly change due to heat loss. Furthermore, the evaporation speed is low. It is evident that further studies are necessary to bring a
rate of volatile liquids may be significantly influenced by Stefan better understanding to the role of pool dimensions and buoyancy
flux, which is not taken into account in above CFD models. effects in evaporation of volatile liquid.
Liu et al. (2011) developed a methodology using CFD to simulate
the boiling process of liquid nitrogen. The vaporization rate of a 2. Pool evaporation model and its validation
boiling liquid is governed by the heat transfer phenomena
including conduction, convection and thermal radiation mecha- The mass flow of vapor from the pool surface Jg,s due to evap-
nisms (Ve chot et al., 2013), while the evaporation rate of non- oration was calculated on the basis of the standard wall functions
boiling liquids is controlled by the removal of vapor from the (Fluent, 2006) taking into account the correction for Stefan flow:
pool surface by airflow (van den Bosch, 1997). Thus, for boiling and


non-boiling liquids the using of CFD code is reasonable to improve Yg;s  Yg;P rCm0:25 k0:5
P
the prediction of convective heat and mass transfer, respectively. Jg;s ¼K (1)
Yþ
The present paper aims to validate the developed pool evapo-
ration CFD model using literature and our own experimental data (  
and to study the effect of the pool sizes on the evaporation rate Sc$yþ yþ < yþ
C
þ    ;
Y ¼ (2)
from volatile liquid spill using numerical simulation. In the previ- Sct uþ þ PC yþ > yþ
C
ous work (Galeev et al., 2013a) the pool evaporation model was
validated using only experimental data on liquefied butane evap-
oration. However, before to use a mathematical model in risk rCm0:25 k0:5
P yP
yþ ¼ ; (3)
assessment, the model must be carefully tested against experi- m
mental data from different sources. Therefore, in the present work
we also compared simulation results both with the experimental 1  þ
data on evaporation of ethanol and cyclohexane (Habib et al., 2009) uþ ¼ ln Ey  DB; (4)
k
and with our own experimental data on evaporation of acetone.

8  
>
> 0 Ksþ < 2:25
>
>
>
> !
>
> n  o
<1 Ksþ  2:25
DB ¼ ln þ Cs $Ks $sin 0:4258$ ln Ksþ  0:811
þ
ð2:25 < Ksþ < 90Þ ; (5)
>
> k 87:75
>
>
>
>1    
>
>
: ln 1 þ Cs $K þ Ksþ > 90
s
k

The pool evaporation rate sensitivity due to pool length has not
been fully addressed in the literature. In the work (Khajehnajafi and
Pourdarvish, 2011) the pool size determines the different flow re-
gimes over the flat surface. Depending on the intensity of turbu-
lence in the main stream, the flow near the surface becomes r$Ks $Cm0:25 k0:5
turbulent at some downstream distance (Schlichting, 1968). The Ksþ ¼ P
; (6)
m
point of transition from laminar to turbulent boundary layer flow
may be estimated in terms of the length Reynolds number, " 3=4 #
ReL ¼ ULn1, where U is the main stream air velocity (ms1), L is the PC ¼ 9:24
Sc
 1 ½1 þ 0:28expð  0:007Sc=Sct Þ; (7)
pool length in the direction of the airflow (m) and n is the kinematic Sct
viscosity of air (Nielsen et al., 1995). For the length Reynolds
number, the critical value of 5  105 is often assumed (Incropera



ln 1  Yg;P 1  Yg;s
et al., 2006). The critical values for the length Reynolds numbers K¼ : (8)
from 1  105 to 3  105 have been reported (Pasquill, 1943; Bird Yg;s  Yg;P
et al., 1960; Schlichting, 1968; Coulson and Richardson, 1993; It is assumed that the transition between the fully turbulent
Nielsen et al., 1995). When considering accidental spills, the pool region and the viscous layer near the wall occurs at a value yþ
C of 11,
sizes are large and ReL exceeds the critical value and the prevalence independent of the concentration of the evaporating component.
of turbulent mechanism of the transport of vapor away from the In Eqs. (1)e(6) the coefficient Cm is assumed to be a constant:
evaporating pool is expected. In the model (Mackay and Matsugu, Cm ¼ 0.09. In the gas dispersion model, this coefficient is
 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49
determined by relating Cm to the mean flow deformation as adopted
in the Realizable keε turbulence model (Shih et al., 1995).
The change of local liquid temperature is calculated from the
equation
vTliq qa þ qgrd þ qs  qp þ qar  Jg;s $DHg
¼ ;
vt CP;liq $mliq
where qa is the heat flux from the atmosphere, W/m2; qgrd is the
heat flux from the ground to the liquid, W/m2; qs is the heat flux
from solar radiation, W/m2; qp is the heat flux emitted by the pool
due to long-wave radiation, W/m2; qar is the heat flux absorbed by
the pool due to long-wave radiation from the atmosphere, W/m2
The heat flux from the ground to the liquid phase,
qgrd ¼ lgrd(vTgrd/vy)y¼0 is found from the numerical solution of
three-dimensional nonstationary heat conduction equation for the
substrate as was done in the work (Galeev et al., 2013a, b).
The heat flux from the atmosphere qa is calculated using wall
functions (Fluent, 2006).
The qs, qp, qar were determined from the equations given in the
paper (Kawamura and Mackay, 1987).
The change in liquid mass is calculated from the equation:
vmliq
¼ Jg;s :
vt
The Equations (9) and (10) were incorporated into the CFD code
Fluent as user-defined scalar (UDS) transport equations without
convection and diffusion terms.
Fig. 1. Profiles of (a) velocity U, (b) turbulence kinetic energy k, (c) turbulence kinetic energy dissipation rate ε and (d) turbulent viscosity mt from numerical calculation (solid line)
and from Yang et al. (2009) (dashed line) at the wind velocity of 1 m/s at the height of 10 m.
41
The mass flux Jg,s is used as a boundary condition for the
dispersion model in the pool area. The atmospheric dispersion of
vapor is calculated by solving the three-dimensional Reynolds-
averaged NaviereStokes equations and the energy and species
equations. The governing equations are closed using the Realizable
keε equations for turbulence.
(9)
To calculate the dispersion of vapor in the atmosphere, it is
important to define the correct profiles for the mean velocity, tur-
bulence kinetic energy and its dissipation rate on the inlet to the
computational domain. These inlet profiles should be maintained
throughout a calculation domain. The fully developed profiles
provided by Richards and Hoxey (1993) are mathematically
consistent, i.e. they are a solution of the mathematical models
describing a homogeneous atmospheric boundary layer (Parente
et al., 2011). However, the assumption of constant kinetic energy,
k is not consistent with wind-tunnel measurements (Robins et al.,
2001; Yang et al., 2009) where a variation of k with height is
generally observed. Yang et al. (2009) proposed a new set of inlet
conditions where the k profile is a function of height. Gorle, et al.
(2009) proposed formulations for the turbulence model co-
efficients to ensure stream-wise homogeneity while using the k
profile proposed by Yang et al. (2009). In the present work the inlet
profiles were determined through repeated calculations when the
velocity and turbulence parameters profiles deduced at the outlet
(10) section of the computational domain were set at its inlet boundary
and the computation was repeated until the profiles for outlet and
inlet boundaries were close. The plots in Figs. 1e3 show the com-
parison between calculated profiles and profiles by Yang et al.
42 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49
Fig. 2. Profiles of (a) velocity U, (b) turbulence kinetic energy k, (c) turbulence kinetic energy dissipation rate ε and (d) turbulent viscosity mt from numerical calculation (solid line)
and from Yang et al. (2009) (dashed line) at the wind velocity of 2.5 m/s at the height of 10 m.
(2009). These profiles were obtained at wind velocities of 1, 2.5 and
5 m/s and under neutral atmospheric stability. The plots show that
there is no significant difference in the velocity and ε at the wall
while there is the difference in k. The similar discrepancy between
experimental and simulated profiles of k is observed in the work
(Mokhtarzadeh-Dehghan et al., 2012). At close velocity profiles, the
impact of using different turbulence parameters profiles on the
results of vapor dispersion calculation will be governed by
the parameter mt/Sct. Due to the fact that coefficient Cm ¼ 0.028 in
correlations of Yang et al. (2009) is much lower than the same
coefficient in the used Realizable keε model (is equal to about
0.09e0.14 depending on height from wall), the turbulent viscosities
at the wall practically coincide. By optimizing the value of turbulent
Schmidt number, it is possible to reach a good agreement between
the predicted and measured parameters for both approaches. In the
work (Galeev et al., 2013b), the results of calculation of neutral gas
dispersion with Sct ¼ 0.5 and calculated profiles, agreed better with
experiment data than with Sct ¼ 0.7, whereas in the work (Galeev
and Ponikarov, 2014) the good agreement between simulation
and experiment on heavy gas dispersion was obtained at Sct ¼ 0.7.
In the present work numerical simulations are performed with
calculated profiles for mean velocity and turbulence parameters
and with Sct ¼ 0.7.
To validate the CFD evaporation model, the predicted results
were compared with the experimental data obtained by Habib et al.
(2009). They carried out experiments in the open air for evapora-
tion of ethanol and cyclohexane at constant temperatures. One
facility comprised a flat terrain without buildings whilst the other
was situated in a very rough area. The pool consisted of a circular
basin with a diameter of 0.74 m which was insulated from the
ground. The experimental data for cyclohexane are presented in the
work (Khajehnajafi and Pourdarvish, 2011).
The difference between the pool evaporation model used in the
present study and the one used in our previous works (Galeev et al.,
2013a; Galeev et al., 2013b; Galeev and Ponikarov, 2014) is that the
model in the present study takes into account roughness for very
rough area when the roughness height larger than the height of the
centre point of the wall-adjacent cell.
The two parameters of the rough wall model, i.e. the roughness
height Ks and roughness constant Cs, were determined according to
the relationship between Ks, Cs and z0 (Blocken et al., 2007):
KS ¼ 9:793$z0 =Cs : (11)
In the calculation, it is assumed that the aerodynamic rough-
ness of flat terrain z0 is equal to pool surface roughness
z0 ¼ 0.0002 m (Ks ¼ 0.00195 m) and Cs ¼ 1. For the very rough area
the aerodynamic roughness is set equal to 0.04 m (Ks ¼ 0.39 m).
Although in the work (Troen and Petersen, 1989) for area with
many trees and buildings it is recommended to use the value of
z0 ¼ 0.1 m we assumed a lower value to avoid the divergence
problems during iterative process. Ks should be smaller than the
height of the centre point of the wall-adjacent cell. The height of
wall-adjacent cells was 0.1 m, therefore, in the simulation of a very
rough area, the roughness height, Ks, was set to the value of 0.05 m
and from Eq. (11), the corresponding value of constant Cs was 7.83.
Fluent Manual states that constant Cs should be smaller or equal to
1 and it is not possible to set a higher value via a user interface.
Therefore, a higher value is defined through a User Defined
 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49
Fig. 3. Profiles of (a) velocity U, (b) turbulence kinetic energy k, (c) turbulence kinetic energy dissipation rate ε and (d) turbulent viscosity mt from numerical calculation (solid line)
and from Yang et al. (2009) (dashed line) at the wind velocity of 5 m/s at the height of 10 m.
Function. This approach to set roughness parameters in Fluent
was used in the gas dispersion calculation by Labovsky and
Jelemensky (2011).
The computational domain with dimensions 100 m  500 m
 100 m in the x, y, z directions was used. A structured non-uniform
grid consisting of parallelepiped cells was generated. The grid cells
were clustered in the region of the pool. The number of grid cells was
approximately 96,000.
The second-order scheme was used for the discretization of the
advective terms of the governing equations. The PRESTO! algorithm
(Fluent, 2006) to calculate the pressure and the SIMPLE algorithm
(Patankar, 1980) to correlate the velocity field and pressure were
used. The convergence criterion for dispersed material concentra-
tion was 1  104, for other variables was 1  103. The maximum
time step of 2 s was used.
Accuracy of the models was estimated by the value of percent
error (%):
.
d ¼ 100$ Jg;s;calc  Jg;s;expt Jg;s;expt :
Tables 1 and 2 show experimental data and prediction values for
evaporation of ethanol and cyclohexane at different temperatures
and wind speeds. The computed values of the Mackay-Matsugu
equation are obtained with a difference d to the measured ones
between 27.5 and 61.1%, with an average value of 47.4%. The
computed values of the numerical model are obtained with a dif-
ference d to the measured ones between 0.6 and 47.4%, with an
average value of 12.7%.
43
To validate the evaporation model, our own experimental data
for acetone evaporation were also used. The liquid was poured into
the pan with sizes of 0.6 m  0.4 m  0.035 m. The air velocity was
measured at the height of 2 m by an acoustical anemometer with an
error ± 0.2 m/s. An averaging time of the wind speed was 2 min. To
measure the change in mass of the pan with the liquid, the Mettler-
Toledo XP8002S balance was used with an accuracy of 0.01 g. To
measure the temperature of the liquid the thermocouple chromel-
copel with an accuracy of 0.1  C was used.
The measurements were carried out at the air temperature of
23  C and humidity of 40%. The initial temperature of acetone was
equal to 23.5  C. Wind speed was varied during the experiment
(Fig. 4). In the calculation the average wind speed for the consid-
ered time period was used, which was equal to 1.05 m/s. The solar
flux was determined using the equation given in the paper
(Kawamura and Mackay, 1987), with taking into account the lati-
tude and longitude of terrain and cloud cover, and its value was
430 W/m2. The heat fluxes due to the long-wave radiation of the
atmosphere and the pool surface have been taken into account
(12) through the use of formulae from the same source. The heat flux
from the ground is assumed to be equal to zero because the pan
with liquid was placed on the balance. The aerodynamic roughness
of the area around the pool is set equal to 0.01 m (Ks ¼ 0.098 m),
that corresponds to the area with short grass (Troen and Petersen,
1989).
Fig. 5 shows that the model somewhat underestimates the
evaporated mass. The difference between the measured and
calculated evaporated mass is 17.5%. The difference between
44 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49

Table 1 3. Sensitivity study and discussion

Experimental data and predictions for ethanol evaporation.

Pool temperature, К Wind velocity at Mass flow, g/s This section presents the numerical analysis of the effect of pool
2 m height, m/s
Experiment Mackay e CFD model
sizes on evaporation of hexane. Hexane has high volatility (at a
Matsugu Eq. liquid temperature of 303 К the hexane vapor pressure is equal to
25 kPa) and hexane vapor is 3 times heavier than the ambient air.
Flat terrain
310.15 1.4 0.456 0.681 0.393 These factors affect pool evaporation and vapor cloud dispersion
309.65 1.9 0.533 0.855 0.523 processes. The pools with sizes of 10 m  10 m, 30 m  30 m,
325.15 1.7 1.02 1.59 1.06 60 m  60 m and 100 m  100 m are considered. The initial liquid
Very rough terrain
layer height was equal to 0.05 m. The initial temperature of ambient
305.65 1.4 0.488 0.663 0.536
310.15 1.8 0.679 0.99 0.9 air and pool substrate was 303 K. The numerical study included a
324.65 1.8 1.32 1.95 1.96 series of calculations at wind speeds 1, 2.5 and 5 m/s at the height of
10 m. The solar flux had a range of 0e900 W/m2 (Khajehnajafi and
Pourdarvish, 2011), therefore in calculation the average value
qs ¼ 450 W/m2 was used.
Table 2
Experimental data and predictions for cyclohexane evaporation. The geometry of the computational domain is shown in Fig. 6.
The calculation was performed for half of the pool because of
Pool temperature, К Wind velocity at Mass flow, g/s
symmetry of the problem. The computational domain with di-
2 m height, m/s
Experiment Mackay e CFD model mensions 2000 m  500 m  500 m in the x-, y-, z-directions was
Matsugu Eq.
used. A structured nonuniform grid consisting of parallelepiped
Flat terrain cells was generated. The number of grid cells was approximately
303 2.71 1.08 1.74 1.11 370,000. The height of wall-adjacent cells was equal to 0.2 m. In
310 3.05 1.63 2.49 1.66
317 3.49 2.33 3.63 2.55
downwind (x-axis) and crosswind (z-axis) directions, the grid cell
Very rough terrain size was 1 m over the pool surface. Additionally to the above
303 1.71 0.967 1.39 1.15 domain, a domain under the pool containing the ground of 2 m
310 1.62 1.35 1.80 1.46 depth was also included for in the calculations. The profiles of wind
317 1.4 1.67 2.13 1.68
velocity, k and ε on the inlet to the computational domain (plane
ABCD) were obtained through calculation and are shown in
Figs. 1e3. On the lateral and upper boundaries (ABFE, BCGF and
experimental and predicted dependencies of liquid temperature DCGH) of the domain the symmetry condition was specified, i.e.
is explained by the difference in evaporation rates. It should be velocity component normal to the boundary and normal de-
noted, that up to about 10 min, the experimental and calculated rivatives of the other variables assumed to be equal to zero. The
values of the mass and temperature are close, although the wind bottom boundary (ADHE) was defined as a no-slip wall. At the
velocity in calculation (1.05 m/s) was about 2.5 times greater outlet boundary (EFGH) the gauge pressure was fixed at zero. The
than the one in the experiment. This could be explained by the view of used computational grid near the pool is shown in Fig. 7.
fact that at very low wind speeds and at the small pool size the The roughness coefficient value Cs ¼ 1 was applied in this study.
molecular mechanism of vapor removal from the evaporation The roughness height Ks for the pool surface was given as
surface could dominate, when the sensitivity of evaporation to 0.00195 m and for the adjacent territory was 0.098 m. The liquid
wind velocity is not as high as in the turbulent regime. temperature was imposed as a thermal boundary condition on the
Conventionally, the Sherwood number, Sh, (the dimensionless wall under the pool while the wall around the pool was considered
parameter describing the mass transfer) is proportional to Re0.5 adiabatic.
for laminar flow over a flat surface, while Sh ~ Re0.8 in turbulent In the simulation, it was assumed that physical properties of
flow (Incropera et al., 2006). liquid, gas and solid layer did not depend on temperature. The
following values have been used: Dm,g ¼ 6.9$106 m2/sec;
mg ¼ 6.6$106 kg/(m sec); ma ¼ 1.78$105 kg/(m sec); CP,g ¼ 1680 J/
(kg К); CP,a ¼ 1006 J/(kg К); CP,liq ¼ 2300 J/(kg К); lg ¼ 0.013 W/
(m К); la ¼ 0.0242 W/(m К); DН g ¼ 370,000 J/kg; lgrd ¼ 1.28 W/
(m К); С P,grd ¼ 1130 J/(kg К); rgrd ¼ 2300 kg/m3. Here, the Dm, m, CP,
l, r, denote molecular diffusion coefficient, molecular viscosity,
specific heat, thermal conductivity and density, respectively. The a,
g and grd subscripts indicate air, evaporating gas and ground value,
respectively.
The vapor pressure Pg of hexane as a function of liquid tem-
perature Tliq was determined using the formula (Green and Perry,
2008):

   .   
E
Pg Tliq ¼ exp A þ B Tliq þ C$ln Tliq þ D$Tliq ; (13)

where A ¼ 104.65, B ¼ 6995.5, C ¼ 12.702, D ¼ 0.000012381,

E ¼ 2.
In Fig. 8 the plots of specific evaporated mass mvap and volume-
averaged liquid temperature Tliq against time are presented. The
plots show that the specific evaporated mass is higher when the
Fig. 4. Measured wind velocity. pool sizes are larger, in other conditions being equal. The influence
 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49
Fig. 5. Measurements (dashed line) and predictions (solid line) of liquid mass and temperature.
Fig. 6. Schematic representation of the computational domain.
Fig. 7. The computational grid near the pool.
of pool sizes on the evaporation decreases when the wind velocity
increases. As the pool sizes increase the vapor concentration above
the surface of the evaporating liquid and, consequently, the vapor-
air cloud density increases. The negative vertical density gradient
appearing above pool surface causes the suppression of turbulence
(stable stratification) that creates a large resistance to the transport
of vapor away from the evaporating pool and results in a slow
45
evaporation rate. In addition to the buoyancy effect, the increasing
of vapor concentration above the pool surface reduces the driving
force of the evaporation. The graphs of temperature change are
consistent with the time dependence of mvap. A higher evaporation
rate results in a lower pool temperature, since the heat losses in-
crease with the increasing of evaporation rate. At the wind velocity
of 1 m/s, the temperature rises throughout the considered period of
time because heat flux from the sun to pool prevails over the heat
losses due to evaporation.
The regression analysis of numerical results has shown that at
the wind speed of 1 m/s the average specific evaporated mass de-
pends on a pool size as mvap ~ L0.553 with accuracy of approxi-
mation of R2 ¼ 0.9981, at wind speed of 2.5 m/s as mvap ~ L0.318
(R2 ¼ 0.9153) and at wind speed of 5 m/s as mvap ~ L0.0578
(R2 ¼ 0.9755). Thus, at low wind velocities the stronger dependence
of evaporation rate on pool size is observed, than the one
(mvap ~ L0.11) adopted in the Mackay-Matsugu equation commonly
used in hazard assessment (Kawamura and Mackay, 1987; Mackay
and Matsugu, 1973).
Table 3 presents the values of the physical properties of gases
and liquids for the upper and lower limits of the variation range of
liquid temperature. At these temperatures the physical properties
do not differ significantly, that confirms the validity of the
assumption of constant physical properties. The molecular diffu-
sion coefficient was determined using Gilliland's correlation
(Gilliland, 1934) and other values were taken from the ChemCAD
program database.
In Fig. 9 the time dependences of the relative turbulent viscosity
and the driving force (DYg ¼ Yg,s-Yg,P) are shown. The relative tur-
bulent viscosity is defined as the dynamic coefficient of average
turbulent viscosity above the pool surface (y ¼ 0.1 m) divided by
the turbulent viscosity in the absence of the disturbing effect of the
source. The relative turbulent viscosity for an undisturbed flow
(when there is no hexane vapor) is equal to 1.0 for each of the wind
velocities. In the initial period of evaporation, a sharp decay of
turbulent viscosity occurs due to the formation of the negative
density gradient above pool surface. The importance of buoyancy
effect rises as the air velocity decreases and pool sizes increase. The
slight growth of the eddy viscosity at wind speeds of 2.5 m/s and
5 m/s is attributed to the reduction of liquid temperature, and, as
consequence, the reduction of mass flux of vapor from the pool
surface.
At low wind velocities, the driving force of evaporation signifi-
cantly drops as pool sizes increase due to the increasing of the
concentration above the pool surface. Since in the model the
driving force is both in the numerator and the denominator of the
46 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49

Fig. 8. Dependencies of specific evaporated mass (left) and average liquid temperature (right) against time at wind velocities of 1 m/s (a), 2.5 m/s (b) and 5 m/s (c).

formula for the diffusion flux, its effect on the evaporation rate
Table 3 will be determined by the factor ln((1Yg,P)/(1Yg,s)). At the wind
Physical properties of gases and liquid.
speed of 1 m/s when the pool sizes increase from 10 m  10 m to
Physical property Temperature, K Variation, % 100 m  100 m the average factor reduces by 11%, at the wind speed
286 308 of 2.5 m/s e by 6.4% and at the wind speed of 5 М/с e by 3.5%, while
average specific evaporated mass mvap reduces by 71.5%, 53% and
Dm,g, m2/sec 6.48$106 7.24E-06 11.7
mg, kg/(m sec) 6.5$106 6.7$106 3.1 12.8%, respectively. Thus, changes in the evaporation rate with
ma, kg/(m sec) 1.78$105 1.88$105 5.6 increasing of pool sizes are determined mainly by the effect of
CP,g, J/(kg К) 1590 1690 6.3 turbulence suppression over the pool surface, and not by changes in
CP,a, J/(kg К) 1005 1008 0.3 the driving force.
CP,liq, J/(kg К) 2215 2310 4.3
lg, W/(m К) 0.0115 0.0135 17.4
In the paper (Britter, 1989), a criterion that indicates when the
la, W/(m К) 0.024 0.026 8.3 plume may be considered passive, i.e. when the influence of the
DН g, J/kg 380,000 362,500 4.6 density difference on the inertia small and may be neglected, is
given. For continuous source this criterion is
 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49 47

Fig. 9. Dependencies of average relative turbulent viscosity (left) and driving force (right) at wind speeds of 1 m/s (a), 2.5 m/s (b) and 5 М/с (c).

In Table 4 the values of B и Ric for each of considered cases are

 1=3 .
B ¼ g00 $q0 L U  0:15;
where g00 ¼ gðrg  ra Þ=ra ; q0 is the volume flow rate; L is the source
dimension and U is the ambient velocity.
For determining the relative importance of the flow regimes
(buoyancy-dominated, stably stratified and passive dispersion) the
Richardson number, Ric, is also used (Havens, 1992):
. appreciable suppression of turbulence (stable stratification) above
Ric ¼ g00 $H u2* ;
where H ¼ q0/UL is the characteristic cloud height and u* is the
friction velocity
If Ric  30 the flow is negative buoyancy dominated, if
1Ric  30, the shear flow is stably stratified and if Ric  1 the
passive dispersion occurs (Havens, 1992).
(14) given. In the calculation of these criteria, the average values of
the gas flow rate have been substituted in expressions (14)
and (15).
The values of Britter's criterion are less than 0.15 only when the
pool sizes are 10 m  10 m and the wind speed is 5 m/s. This result
is confirmed by the graphs (see Fig. 9), which show that the change
of turbulence due to buoyancy effects is small at wind speed of 5 m/
s and at the pool sizes of 10 m  10 m, while in the rest cases the
(15) pool surface takes place. Generally, at the wind speed of 5 m/s the
Britter's criterion is less, or slightly greater than the critical value,
whereas at low wind speeds and extended pools it significantly
exceeds the critical value. The values of Richardson number are also
consistent with the numerical calculations. The Ric in most cases is
in the range from 1 to 30 indicating the prevalence of stably
stratified shear flow. The Ric < 1 is obtained only for the case where
48 A.D. Galeev et al. / Journal of Loss Prevention in the Process Industries 38 (2015) 39e49

Table 4 yP normal distance from the pool surface to the neighboring

Values of B and Ric depending on pool sizes and wind velocity. node of the computational grid
Pool sizes Britter's criterion B (Richardson number Ric) z0 aerodynamic roughness, m
1 m/s 2.5 m/s 5 m/s
Greek symbols
10 m  10 m 0.35 (12.4) 0.20 (2.2) 0.12 (0.5)
30 m  30 m 0.42 (20.3) 0.27 (5.5) 0.17 (1.3)
ε turbulence kinetic energy dissipation rate, m2/s3
60 m  60 m 0.46 (26.7) 0.31 (8.4) 0.21 (2.6) k von Karman constant equal to 0.41
100 m  100 m 0.51 (35.9) 0.33 (10.3) 0.25 (4.1) l coefficient of thermal conductivity, W/(m K)
m coefficient of molecular viscosity, kg/(m s)
mt coefficient of turbulent viscosity, kg/(m s)
the pool sizes are 10 m  10 m and the wind speed is 5 m/s and r density, kg/m3
Ric > 30 is obtained when the pool sizes are 100 m  100 m and the
wind speed is 1 m/s. Subscripts
no index vapor-air mixture
a air
4. Conclusion g evaporating component
grd ground
The validation of the developed pool evaporation CFD model liq pool
against both literature and our own experimental data is per- P centroid of the wall-adjacent cell
formed. A good agreement is obtained between the measured and s surface of pool
the predicted evaporation rates. Based on the proposed model a
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