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CORRELATIONS
Empirical correlations are presented for the density and viscosity of aqueous formaldehyde
solutions as a function of temperature (T) and overall weight percentage of formaldehyde (WF).
Experimental density data from the literature, at T ) 288-338 K and with WF ) 1.6-50 wt %,
are described with an average absolute residual (AAR) of 0.14%. Experimental viscosity data,
both new and from the literature, at T ) 288-333 K and with WF ) 1.6-50 wt %, are described
with an AAR of 1.8%. The residuals of the correlations are free of trending effects as a function
of T and WF. It is shown that both properties can be described using liquid mixture correlation
methods from the literature with almost the same accuracy relative to the empirical correlations.
mentioned in Table 1:
x FMF
WF ) 100% (6)
x FMF + (1 - x F)MW
The experimental results show that Fm varies with T Figure 1. Density difference between aqueous formaldehyde
and WF and that always Fm > FW (for WF > 0). Figure 1 solutions and water, both at the same temperature. Fm: from the
shows the density difference (Fm - FW) as a function of literature sources indicated. FW: Perry et al.5
WF, with FW from Perry et al.5 It shows that a consider-
able fraction of the observed variation of Fm can be
accounted for by introducing a linear dependency of Fm
- FW on WF. Least-squares regression of the data
accordingly, followed by an analysis of the residuals, i,
defined as
i ) ((Fm)calc - (Fm)exp
(Fm)exp )
i
100% (7)
n
1
AAR )
ni)1
|i| (9)
Figure 3. Relative residuals of the empirical density correlation
(8) as a function of WF showing no trending effects. For symbols,
More importantly, however, the residuals obtained with see Figure 1.
eq 8 do not show any systematic variation with T or
WF; see Figures 2 and 3. Therefore, eq 8 is a reliable
empirical equation for Fm. With eq 42 an AAR of 0.42% calculation of liquid densities of mixtures of similar
(MAX of 1.18%) was observed, which is 3 times as high components,5
as the value of eq 8.
Many literature methods for the calculation of liquid
mixture densities use the critical properties and acentric
factors, i.e., vapor pressure vs temperature correlations,
Vm ) i xiVi (10)
of the individual components6 and are therefore not
suitable here because the required properties of the
higher poly(oxymethylene glycols) (POMs) are unknown. To apply eq 10, the composition of the liquid has to be
Although Amagats law originally holds strictly only for considered. In aqueous solutions, formaldehyde is hy-
mixtures of ideal gases, it is also recommended for the drated to methylene glycol and a series of POMs:
Ind. Eng. Chem. Res., Vol. 39, No. 2, 2000 559
Figure 4. Relative residuals of the density correlation obtained
Vm ) VWxW + (VW + iVF)xWFi (13) from Amagats law (eq 18) as a function of the temperature. For
i)1 symbols, see Figure 1.
i)1
ixWFi
x F ) (15) Figure 5. Relative residuals of the density correlation obtained
from Amagats law (eq 18) as a function of WF. For symbols, see
xW + (i + 1)xWFi Figure 1.
i)1
and the substitution V ) M/F, eq 13 can be rewritten of T, varying in the expected direction, i.e., from
as negative values at the lower temperatures to positive
values at the higher temperatures.
Mm MW x F Because of the clear trend of the residuals, a second
) + V (16) parameter to account for the influence of T on VF seems
Fm FW 1 - x F F justified. Least-squares analysis of the experimental
data according to eq 18 resulted in the following
Because every molecule in the solution is either a free optimum parameters for VF:
water molecule or a water molecule chemically bonded
to one or more formaldehyde units, the true total
concentration in the solution is equal to the overall VF ) 12.709 10-3 + 30.59 10-6T (19)
water concentration. Therefore, the true mean molar
weight of the solution, Mm, can be obtained as Figures 4 and 5 illustrate the relative residuals of Fm
calculated with eqs 18 and 19 as a function of WF and
MW T. No trend in the residuals was found. Here, an AAR
Mm ) (17) of 0.22% was found (MAX of 0.69%).
1 - (WF/100)
At first glance, eqs 8 and 18 might seem paradoxical:
eq 8 correlates Fm linearly with WF, while eq 18
and the model equation for the density of aqueous
correlates 1/Fm similarly. This is not a true inconsis-
formaldehyde solutions, from inserting eqs 6 and 17 in
tency, because the coefficient of WF is positive in eq 8,
eq 16 and rewriting, becomes
resulting in an increase of Fm with an increase of WF,
100FWMF whereas the overall coefficient of WF in the denominator
Fm ) (18) of eq 18 is negative, giving the same direction of
(100 - WF)MF + FWWFVF variation of Fm with WF.
The only parameter in eq 18 to be determined from the Viscosity
experimental data is the molar volume of the CH2O
groups in the POM molecules, VF. By taking VF con- Table 2 summarizes literature data on the viscosity
stant, an AAR of 0.45% was obtained (MAX of 1.7%). of aqueous formaldehyde solutions. Because this data
Not surprisingly, however, taking VF constant resulted set is rather limited, we performed additional viscosity
in a clear trend of the residuals of eq 18 as a function measurements with a Schott automated viscosity meter
560 Ind. Eng. Chem. Res., Vol. 39, No. 2, 2000
ln ( )
m
FmMm
) -47.90 +
5644
T
+ 9.36
Figure 9. Viscosity of poly(ethylene glycols), HO(CH2CH2O)iH, Figure 10. Viscosity of aqueous formaldehyde solutions. Sym-
as a function of the molecular size i at various T. Symbols: bols: experimental data; see Figure 6. Lines: calculated with eq
experimental values from the sources indicated. Lines: calculated 24.
with eq 22.
ln PEGi ) a + ib (22)
ln WFi ) A + iB (23)
x F
ln m ) xW ln W + (1 - xW)A + B (24)
1 - x F