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 acquire just the cations (Fe, Mg, Ca, etc.) intensities 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.
The following is an analysis example of carbon calculated by stoichiometry to oxygen in a carbonate sample for an oxide run :
Analysis of sample st 135 set 2 calcite (analyzed)
Total Number of Data Points = 5 Number of "G" Data Points = 5
Average Beam Counts = 45527. Average Base Time = 10.00
Average Sample Z-bar = 12.572 Average BNA Iterations = 11.000
Element : C is Calculated Relative to Stoich. Oxygen at .333 to 1.0 Atom
Results in Weight Percent :
CO2 Cl MgO FeO MnO O SUB
SPEC 43.82 .00 .00 .00 .00 .00 43.82
SDEV .19 .00 .00 .00 .00 .00
BGD: MAN MAN MAN
CaO SO3 P2O5 SUM
29 55.60 .01 -.01 99.12
30 56.18 .04 -.01 100.22
31 56.16 .01 .00 100.10
32 56.02 -.01 -.02 99.77
33 56.10 -.01 .01 100.00
AVER 56.01 .01 -.01 99.84
SDEV .24 .02 .01
SERR .11 .01 .00
PUBL 56.01 n.a. n.a. 99.90
%VAR .00 .00 .00
*
BFAC 1.0314 .9925 1.0285
KRAW 1.0001 .0001 -.0001
P/B: 277.12 1.02 .87
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! The following is an example of how this calculation looks :
Analysis of lines:
23 24 25 26 27 28 29 30
Total Number of Data Points = 8 Number of "G" Data Points = 8
Average Beam Counts = 98504. Average Base Time = 10.00
Average Sample Z-bar = 10.816 Average ZAF Iterations = 5.000
Element : Al is Calculated Relative to Stoich. Oxygen at .666 to 1.0 Atom
Element : O is Calculated by Stoichiometry
Results in Weight Percent :
Se O Al Si SUB
SPEC .00 46.68 52.41 .05 99.14
SDEV .00 .02 .02 .00
BGD: OFF OFF OFF
Zn Cu Pd SUM
23 .59 .30 .01 100.02
24 .56 .30 .01 100.02
25 .57 .32 .00 100.02
26 .58 .33 .00 100.02
27 .53 .33 .02 100.02
28 .55 .39 .01 100.02
29 .54 .26 .00 100.02
30 .56 .31 .01 100.02
AVER .56 .32 .01 100.02
SDEV .02 .04 .01
SERR .01 .01 .00
KRAT .0047 .0027 .0000
ZCOR 1.2009 1.1976 1.2321
KRAW .0093 .0027 .0000
P/B: 2.70 2.29 1.02
%INT -.05 .00 .00
Results in Oxide Weight Percents using Custom Cation Oxide Ratios :
Se O Al2O3 SiO2
AVER .000 .000 99.029 .107
SDEV .000 .000 .040 .000
Zn Cu Pd SUM
23 .592 .302 .006 100.022
24 .556 .300 .015 100.022
25 .574 .323 .000 100.022
26 .581 .330 .000 100.022
27 .528 .332 .018 100.022
28 .550 .386 .008 100.022
29 .543 .262 .001 100.022
30 .561 .308 .013 100.022
AVER .561 .318 .008 100.022
SDEV .021 .035 .007