5.3.4.

Effect of other variables on gas-liquid mass transfer

The other important valuables are the diffusion coefficients kg and kL, which can be varied
considerably by the character of the absorption process. Any factors which tend to cut down
the thickness of the surface films should increase the coefficients and correspondingly speed
up the absorption rate. The effect of such factors will be somewhat dependent upon whether
the process is controlled by gas film or liquid film diffusion. High liquid velocity increases
the diffusion through the liquid film, whereas high gas velocity increases diffusion through
the gas film. Furthermore, the influence of such other variables as velocity, temperature, and
the like must be identical for different diffusing substances.

5.3.4.1. Effect of fluid temperature

Changes in temperature affect several factors, and it is necessary to distinguish clearly

between the effect of temperature on the equilibrium and its effect on the coefficients of
diffusion. Increase in temperature makes the gas less soluble, thus tending to lower the rate of
absorption. The diffusion coefficients themselves may, however, be either raised or lowered
by temperature, depending upon changes in film thickness and in specific diffusivity.

Liquid film coefficients, kL, rise rapidly with increasing temperature, both because of
decreased film thickness due to lowered viscosity and because of greater diffusivities. On the
other hand, Haslam, Hershey, and Kean show that the gas film coefficients, kg, decrease
somewhat as the temperature rises because the ratio of density to viscosity for the gas
decreases and therefore the gas film becomes thicker. Although little is known regarding the
effect of temperature on specific diffusivities through gas films, it seems evident that this
effect is less than that due to an increase in the film thickness.

5.3.4.2. Effect of apparatus type

A type of apparatus in which gas bubbles up through a liquid would represent vitally different
conditions from one where liquid drops are sprayed through a gas. In the first instance, a
rising gas bubble would continuously expose fresh liquid surface and the conductivity of the
liquid film would be high, whereas the gas film would be relatively undisturbed. Such a
device should therefore be most satisfactory for absorbing the less soluble gases where liquid
film diffusion is controlling. In the other case, a falling drop might be expected to have only a
very thin gas film but a fairly thick liquor film. Apparatus of a spray type might therefore be
well suited for absorbing very soluble gases. From these suggestions it is evident that the
 k 
ratio of film conductivities  L  varies with the type of apparatus and with the conditions of
 kg 
 
operation. It is therefore quite possible that the absorption of a gas of intermediate solubility
might be controlled primarily by liquid film diffusion in one piece of equipment and by gas
film diffusion in another. This point is illustrated later by the case of sulfur dioxide, which is
almost entirely governed by the liquid film when passed over a free surface of liquid, but
which is largely affected by the gas film when absorbed by bubbling through water. It is
possible to predict comparative performances of different solutes in the same equipment on
the basis of this general concept.

5.3.4.3. Effect of concentration of the diffusing gas

Under similar operating conditions the effective film thicknesses will in most cases be
independent of the solute that is being absorbed. It has been shown that for low
concentrations of the diffusing component there is a definite relationship between the
coefficient of diffusion of material through a gas film and the coefficient of diffusion of heat
through the same film. The total gas pressure and character of the inert gas are also involved
in such a way that the coefficient varies inversely with the product of the molecular weight of
the inert gas and the total pressure. This relationship is based upon a thermodynamic analysis,
which is believed to be valid so long as the concentration of the diffusing component relative
to that of the interfering gas is low. In other words, we have dependable information as to the
change of the gas film coefficient with changes in solute, inert gas, and total pressure.

5.3.4.4. Effect of molecular weight of the diffusing gas

It is known that as the molecular weight of the diffusing material becomes high its diffusivity
decreases, but the data show clearly that the change in diffusivity is small compared with that
in molecular weight. In the absence of more definite information the authors have elected to
assume that the liquid film coefficient follows the same rule as that just given for the gas
film. In the units here employed this means that the liquid film coefficient, kL, under
conditions of equal film thickness, is the same for all substances. This approximation is
somewhat justified by the fact that diffusivity data given in the literature show a surprisingly
small variation for various weak electrolytes and other aqueous solutions of low molecular
weight.