The rate is often controlled by two processes in series--usually the chemical

reaction and liquid-phase mass transfer. The rate in this case can be obtained
by equating the fluxes given by Eq 8 and 9 and solving for the surface
concentration as indicated in Ref 5.
The rate of the nitrogen reaction with iron alloys containing oxygen, sulfur,
chromium, and other elements has been measured by many investigators,
and there is good agreement in most cases (Ref 6, 7, 8, 9, 10, 11). However,
the rate for carbon-saturated iron containing other elements was not
investigated until recently (Ref 12).
In this work, an isotope exchange technique was used to measure the rate of
dissociation of the nitrogen molecule (N2). In particular, the effects of carbon,
sulfur, phosphorus, lead, tin, bismuth, and tellurium on the rate were
investigated.

Sulfur, phosphorus, lead, bismuth, and tellurium decreased the rate, while
carbon and tin had no significant effect. For example, the effect of sulfur is
shown in Fig. 2 as the rate constant versus the reciprocal of the activity of
sulfur (Ref 11). The activity of sulfur is in weight percent, and the activity
coefficient of sulfur in carbon-saturated iron is 6.3. The rate for carbon-
saturated iron with no sulfur is about 10-5 mol/cm2 s atm at 1450 C (2640
F). For example, for 0.009% S (1/as = 18), the rate is decreased to 8 10-7
mol/cm2 s atm. Bismuth and tellurium had an even larger effect (Ref 12),
as shown in Fig. 3 and 4. The activities are relative to pure bismuth and
tellurium, respectively, which have larger deviations from ideal behavior. As
little as 50 ppm Te reduced the rate by 90%, and 50 ppm Bi decreased it by
80%.

On the other hand, carbon is not surface active and does not affect the rate
at moderate sulfur contents (0.017% S) up to 4.5% C (Ref 12), as shown in
Fig. 5. Therefore, the initial rate of nitrogen formation is primarily controlled
by chemical kinetics at the surface, and surface-active elements, such as
sulfur and tellurium, can reduce the rate. This information can be helpful in
controlling the rate of the reaction. For example, if it is desired to remove
nitrogen by argon gas flushing, the concentrations of these elements should
be as low as possible. On the other hand, it may be possible to retard
nitrogen evolution during solidification by the deliberate addition of these
elements.

Reactions During Solidification. During the solidification of most simple iron

alloys, there is enrichment of the alloying element because there is greater
solubility in the liquid than in the solid. The difference in the solubilities is
expressed by the partition ratio kS/L, which is determined from the slopes of
the solidus to liquidus lines on the phase diagram. For most simple alloys, the
partition ratio is less than 1, resulting in liquid enrichment during
solidification. For example, for an Fe-0.02N alloy, the last portion of liquid to
solidify will be enriched and will have a concentration of 0.045% N, which is
the solubility of nitrogen in liquid iron at 1 atm (Ref 13). Therefore, even
though the liquid alloy is far from being saturated with nitrogen, during
solidification, the concentration will increase to the point where the solubility
is exceeded and nitrogen gas will be evolved.
Researchers have measured the partition ratio for nitrogen in high-carbon
iron alloys (Ref 4). The partition ratio was found to be 1.9 and 2.2 for stable
and metastable eutectic solidification, indicating that there is greater
solubility in the solid than in the liquid. Therefore, in this case, as the alloy
solidifies, nitrogen is actually enriched in the solid, and the nitrogen content
decreases in the liquid. It may appear that, because there is no enrichment
during solidification, the thermodynamic pressure of nitrogen cannot
increase. The thermodynamic pressure is defined by an expression similar to
Eq 6. Carbon greatly increases the activity coefficient of nitrogen in the liquid
and decreases its solubility; therefore, the thermodynamic pressure may
increase because the carbon content of the liquid is increasing during
solidification.