Professional Documents
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437–445, 2001
Published by Elsevier Science Ltd on behalf of British Occupational Hygiene Society
Printed in Great Britain.
PII: S0003-4878(00)00082-X 0003-4878/01/$20.00
Spreadsheet and short-cut methods have been developed for predicting evaporation rates
and evaporation times for spills and constrained baths of chemical mixtures. Steady-state
and time-varying predictions of evaporation rates can be made for six-component mixtures,
including liquid-phase non-idealities as expressed through the UNIFAC method for activity
coefficients. A group-contribution method is also used to estimate vapor-phase diffusion coef-
ficients, which makes the method completely predictive. The predictions are estimates that
require professional judgement in their application.
One application that the evaporation time calculations suggest is a method for labeling
chemical containers that allows one to quickly assess the time for complete evaporation of
spills of both pure components and mixtures. The labeling would take the form of an evapor-
ation time that depends on the local environment. For instance, evaporation time depends
on indoor or outdoor conditions and the amount of each chemical among other parameters.
This labeling would provide rapid information and an opportunity to premeditate a response
before a spill occurs. Published by Elsevier Science Ltd on behalf of British Occupational
Hygiene Society
thin film (i.e., the bulk vapor concentration, cbi , is The diffusion coefficients are assumed to be binary
negligible). Mathematically, this transport is coefficients, with the second vapor-phase material
described by a balance equation on the number of being air. This assumes that the individual binary
moles of component i, Ni, as coefficients are independent of each other.
To calculate vapor-phase concentrations at the
dNi
= ⫺Aji (1) interface, which are needed in the mole balance
dt above, first the vapor–liquid equilibrium calculations
must be performed for the liquid components. (Air is
where t is time, A is the interfacial surface area, and assumed to be only in the vapor phase.) At low press-
ji is the molar flux of i in moles per area per time. An ures vapor–liquid equilibrium is described by
assumption made here is that the surface area remains Pyi = Poigixi
cosity (n = m/r) of air (far) above the chemical spill Ni = Ni0e⫺t/t̄i (11)
and L is the length of the spill (L = A1/2). Note that
a difference in the diffusion coefficient for a chemical
leads to a slightly different film thickness. In this where t̄i is the time constant for first order decay. To
work r = 0.001161 g/cm3 and m = 0.000186 g/cm/s, approximate the total evaporation time, the time for
(Lide, 1997, 6-1, 6-194). For a turbulent boundary 95% evaporation is used, which defines the evapor-
layer the film thickness is ation time for dilute substances as, ti,dil = 3t̄i, or
L VT0 RT NT0
ltur = (7) ti,dil = 3 (12)
0.0365(UL/n)4/5 Ak̃i Poigi VT0
冘
concern for evaporating mixtures. Nielsen and Olsen
where VT0/NT0 = xm,0MWm/rm). Equation (10) is reported experimental evaporation rates which we
m compare to calculated values from a spreadsheet.
first order in Ni, which results in an exponential decay (The effects of time step size are analyzed in Appen-
equation of the form dix B.)
Evaporation rates and times for spills 441
Table 1. Comparisons of experimental versus calculated rates of evaporation and spreadsheet versus ti-estimated times
for evaporation. Calculations follow the experiments of Nielsen and Olsen (1995), with the exception that the results for
n-butylacetate/water were calculated for a 10-min instead of a 15-min period. Air velocities were 0.17 m/s, the temperature
was 300 K, and the pressure was 101.3 kPa
Chemical Liquid pool Mole fraction Evaporation rate (mmol/m2/s) Evaporation time estimate(s)
mixture L×W×D (mm) xi,0
Table 1 shows that our calculated evaporation rates and Eqs (12) and (14) are fairly precise, as the differ-
are consistently higher than the experimental values. ences between the two columns of Table 1 average
For substances in abundance (xi,0 = 0.9) the average 10% (excluding the dilute ethanol and 2-butanone
over-prediction is 60%. One could fit these results by cases discussed above). To a certain degree, the simi-
changing the coefficients in Eqs (6) and (7) for calcu- lar results can be expected since the same model is
lating the film thickness, however the relationship used as the basis of both methods, however, the τi
between the model and experimental results may vary estimates do not require integration and are very sim-
for different conditions and (combinations of) chemi- ple and quick compared to the spreadsheet calcu-
cals. For dilute substances the experimental evapor- lations. Thus, without doing the iterative calculations
ation rates are over-predicted by an average of 110%, of the spreadsheet one can obtain an evaporation time
and the same caveats apply to fitting these results. estimate of similar precision.
Note that correction terms, described in Nielsen et al. An interesting result of the analysis shown in Table
(1995), could be applied for variable density, bulk 1 is that, except for very dilute mixtures, the evapor-
flow and entrance length. The focus here is on quick ation time for the abundant substance is a reasonable
estimates of rates and times. approximation for the evaporation time of a dilute
The last two columns of Table 1 show estimates substance. For the examples of Table 1 where
of total evaporation times. Values in the first of these
xi,0 = 0.10 the spreadsheet times for abundant and
columns were found through a repetitive spreadsheet
dilute substances differ by an average of 27% (with
application of Eq. (9), while the values in the last
differences ranging 3–56%). Therefore, instead of
column were determined from Eqs (12) and (14). In
needing to know all about a spill (e.g., exactly how
analyzing the results we will first examine the anom-
much of each chemical, etc.), the above result sug-
alies for the two cases involving ethanol and 2-but-
anone. Only in these cases is the evaporation time, ti, gests it may be sufficient to use the abundant subst-
for the dilute substance estimated to be above that for ance as a rough approximation of the evaporation
the abundant substance. In these cases the time for time for the mixture. This generalization is less valu-
evaporation of the dilute substance is too long, and able if one substance is very dilute (e.g.,
the time for the abundant substance as estimated by xi,0 = 5.1×10⫺3) or the relative volatility,
Eq. (14), should be used for both dilute and abun- Podilgdil/Poabugabu, and/or the ratio of mass transfer coef-
dant substances. ficients, k̃dil/k̃abu, are large (as in the cases of ethanol
In general, the results calculated by the spreadsheet in trichloroethylene or water).
442 R. L. Smith
Table 2. Air velocities for outdoor and indoor environments. Outdoor air velocities have been taken from Wood (1998),
and indoor velocities are based on work by the Committee on Industrial Ventilation (1982). Note that the velocities
describing indoor environments are both discontinuous and overlapping (to convert to SI units, 1.0 fpm = 0.0051 m/s and
1.0 mph = 0.45 m/s)
Outdoor winds Air velocities Indoor ventilation
used in this
work (m/s)
cussed. If the evaporation time is long then there is which is similar to Eq. (14) with the exception of
time for a clean up operation, but if the evaporation removing the activity coefficient (and VT0 has been
time is short then there is no time for clean up. The divided out). One can expect that the activity coef-
key to the information transferred as the evaporation ficient for a dilute substance is often far from unity,
time is that it is simple. When confronted with a spill and so the short-cut method for determining the evap-
one has to act quickly. Perhaps the greatest advantage oration time may have a larger error for dilute sub-
of the evaporation time is that it could be memorized stances.
before using the chemical, so that a premeditated For the short-cut method, approximations are made
response is possible. of the diffusion coefficient, the vapor pressure, and
In some uses a particular chemical may be in the calculation of the film thickness. Of course, if
employed in the vicinity of others. In such a case, more accurate values are available for any of these
冘
or heterocyclic ring is present) to obtain a total dif-
method does give order of magnitude estimates that
follow the correct trends. fusion volume (e.g., ni is the total diffusion volume
A
for chemical A). The total diffusion volume is used
CONCLUSIONS in the following equation for the diffusion coefficient
A method for predicting the rates of evaporation of 0.00143T1.75
mixtures has been developed. The results over-predict
the rate of evaporation when compared with labora-
DAB =
1/2
PMAB [( 冘
A
ni)1/3 + ( 冘
B
ni)1/3]2
(A1)
where a time step of 100 s gives nearly the same Lide DR. CRC handbook of chemistry and physics. New York:
results as a 10-s time step. This order of magnitude CRC Press, 1997.
Mackay D, Matsugu RS. Evaporation rates of liquid hydro-
difference in the number of steps is very important carbon spills on land and water. Can J Chem Engng
when repeatedly entering values in a spreadsheet. 1973;51:434–9.
Also, depending on how the results are employed, a Nielsen F, Olsen E. On the prediction of evaporation rates —
1000 s time step might be useful in some circum- with special emphasis on aqueous solutions. Ann Occup Hyg
1995;39(4):513–22.
stances. Note that for simplicity in the spreadsheet
Nielsen F, Olsen E, Fredenslund A. Prediction of isothermal
calculations, Euler’s method was employed to gener- evaporation rates of pure volatile organic compounds in
ate the results, and larger time steps could have been occupational environments — a theoretical approach based
used with a midpoint or fourth-order Runge–Kutta on laminar boundary layer theory. Ann Occup Hyg
method (Press et al., 1989, 547–77). 1995;39(4):497–511.
Poling BE. Personal communication. UNIFAC tables. Univer-
sity of Missouri at Rolla, 1999.
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