# Stoichiometry to Oxygen

#### Stoichiometry to Oxygen

Another useful feature for the analysis of carbonate or borate samples in an oxide run is the use of the "element by stoichiometry to the stoichiometric element (oxygen)" option. With this feature the analyst can analyze just the cations (Fe, Mg, Ca, etc.) in a sample and have the oxygen calculated by stoichiometry and another specified element (usually C for carbonates or B for borates) calculated relative to oxygen. In the case of carbonates, for example CaCO3, carbon is always in the ratio 1 to 3 to oxygen.

Therefore by simply specifying C by stoichiometry relative to the stoichiometric element (oxygen) at 0.333 (1 divided by 3) the correct amount of both oxygen and carbon will be incorporated into the ZAF matrix correction and totals without analyzing for either. This calculation should only be used with compounds where the ratio to oxygen is both known and unchanging.

Note that oxygen must be an analyzed or specified element before this calculation can be applied. One more point about element by stoichiometry to oxygen. Consider the example of a trace element analysis of several metals in an alumina (Al2O3) matrix. If Al and O are not to be analyzed, yet the user desires to have Al2O3 added to the matrix correction, how can this be accomplished?

There are two ways this can be achieved. One way would be to simply specify Al by difference and calculate oxygen by stoichiometry. The program will then correctly add in the proper amount of stoichiometric Al2O3 to the matrix correction for each analysis line. The other way is to use the element by stoichiometry to oxygen calculation as discussed below.

Adjust the cation ratios of the metals to elemental stoichiometry (one cation and zero anions). Next, select "element by stoichiometry to oxygen" and (in this example) select "al" as the element by stoichiometry. To achieve a 2 to 3 ratio, next enter "0.666" Al atoms per O atom. Run the calculation and note that Al2O3 was not added to the matrix calculation! What happened? In this example, the user had selected a cation ratio for the analyzed elements of all elemental atoms, and since there was zero oxygen to begin the iteration, the program never got to add the Al which then never added the stoichiometric oxygen! How can this be avoided? Simply specify some small concentration of an oxide element (for instance SiO2) in the specified element concentration, say 0.05 %. This will give the iteration a chance to get started, and allow it to converge on a very close approximation of the Al2O3 by difference!