EXERCISE 5

Derivation of the Chemical Formula

of a Mineral from its Chemical Analysis

PURPOSE OF EXERCISE The chemical formula of chalcopyrite is CuFeS2, and that

of the alkali feldspar (Na,K)AlSi3O8. The reasons for
Understanding the various steps involved in converting a
reporting some analyses (such as for oxide and silicate
mineral analysis (generally reported in weight percentages
minerals) in oxide form, instead of in elemental form
of elements or oxides) into a mineral formula.
(as was done for analyses 1 through 3), is mainly histori-
cal. Irrespective of the form of the original analysis (be it
FURTHER READING
in elemental or oxide form), one is faced with the question
Klein, C. and Dutrow, B., 2008, Manual of Mineral of how does such an analysis relate to a standard chemical
Science, 23rd ed., Wiley, Hoboken, New Jersey, (mineral) formula?
pp. 99 – 108. A mineral formula such as CuFeS2, or (Na,K)AlSi3O8,
Nesse, W. D., 2000, Introduction to Mineralogy, Oxford records (in chemical shorthand) the ratios of the various
University Press, New York, pp. 71 – 72. elements in the structure. For example, chalcopyrite has
Perkins, D., 2002, Mineralogy, 2nd ed., Prentice Hall, a total of two metal cations (Cu2⫹ and Fe2⫹) and two
Upper Saddle River, New Jersey, pp. 21 – 25. sulfur anions in its structure; this leads to a metal ions:
Wenk, H. R. and Bulakh, A., 2004, Minerals: Their anions ratio of 1⬊1. The alkali feldspar, on the other
Constitution and Origin, Cambridge University Press, hand, has a ratio of five metal ions to eight oxygens as
New York, New York, pp. 258 – 263. deduced from the formula [(Na,K)1 ⫹ ⫹ Al3⫹ ⫹ Si 34⫹ ],
Bloss, F. D., 1994, 2nd printing with minor revisions, that is, 1 ⫹ 1 ⫹ 3 ⫽ 5 cations. Of these, Al and Si sub-
Crystallography and Crystal Chemistry, Mineralogical stitute for each other in a tetrahedral position in the
Society of America, Chantilly, Virginia, pp. 296 – 299. structure (known as the T site). As such, an alkali
feldspar formula could be written as (Na,K)1(Al,Si)4O8.
Background Information: The chemical compositions The Na and K ions are located in a specific position in
of minerals, ranging from simple to complex, are invari- the structure, commonly referred to as the M site, a rel-
ably presented in the form of chemical analyses. Such atively large space outside the Si – Al – O tetrahedral
chemical analyses commonly consist of a listing of the framework.
relative weight percentages of several elements or oxides. This brief introduction to specific atomic locations
Examples of minerals with simple chemical analyses are (“sites”) in crystal structures is very relevant in the con-
version of a weight percent (chemical) analysis to a chem-
1 2
ical formula. Indeed, many silicates have structures
Element Weight % Element Weight %
that are considerably more complicated than those of
Na 39.34 Si 46.75
feldspars; not only may they have a considerable number
Cl 60.66 O 53.25
of sites (the atomic sizes of which are controlled by the
Total 100.00 Total 100.00 packing of oxygen ions about the sites), but they may also
Analysis 1 is for the mineral halite, with the chemical show extensive chemical substitution of various elements
formula NaCl, and analysis 2 is for the mineral quartz, within the same site. For example, a typical pyroxene,
with the chemical formula SiO2. diopside, with formula CaMgSi2O6, contains tetrahedral
Somewhat more complex analyses follow for the miner- sites (known as T sites for the housing of Si4⫹ and Al3⫹)
als chalcopyrite (analysis 3) and alkali feldspar (analysis 4): but also two quite distinct metal (cation) sites, known as
M1 and M2. The principle difference between the two M
3 4 sites is the size of interstitial space between various
Element Weight % Oxide Weight % oxygen atoms; the M2 site is larger than the M1 site.
Cu 34.64 SiO2 65.67 A projection of the typical monoclinic pyroxene structure
Fe 30.42 Al2O3 20.84 is shown in Fig. 5.1.
S 34.94 CaO 0.50 In the various references listed above you will see worked
Na2O 7.59 examples of recalculations from weight percentage analyses
K2O 5.49 to various chemical formulas. This exercise will do much
Total 100.00 Total 100.09* the same, but here we will concentrate on a mineral group,
* Deviations from 100 percent in the analysis total are commonly the the pyroxenes, in which you must make decisions about the
result of experimental error, that is, analytical error. allocation of various cations to the T, M1, and M2 sites, in

Copyright John Wiley & Sons, Inc. 55

56 EXERCISE 5

FIGURE 5.1 The crystal structure of a monoclinic pyroxene across the two M1 sites. These shaded shapes are referred to in
projected down [001], onto the (001) plane, the basal pinacoid. the literature as I-beams. (After M. Cameron and J. J. Papike,
Note the locations of the T, M1 and M2 sites. The shaded areas 1980, Reviews in Mineralogy, vol. 7, Pyroxenes, Mineralogical
outline the infinitely extending Si –O chains that face each other Society of America, Washington, D. C., p. 12).
 DERIVATION OF THE CHEMICAL FORMULA OF A MINERAL FROM ITS CHEMICAL ANALYSIS 57

addition to understanding the steps in converting a weight transformation from weight percentages of the oxides to
percent analysis to a chemical formula. the final chemical formula lead finally to a quantitative
First, you might ask what does a weight percent analysis statement of metal ratios (or chemical subscripts).
mean? The answer to that is that it lists the relative weight However, in order to complete such a transformation
percentages of elements or oxides. To help you understand correctly, we must know something about the feldspar
this answer, we will begin with the formula of chalcopyrite, structure. The largest ions in feldspar are the oxygens
CuFeS2, and work “backward” to a chemical analysis. From (radius of O2⫺ ⫽ 1.40 Å) with cations distributed among
X-ray structural study we know that the unit cell of chal- the various interstitial spaces between the oxygens in close
copyrite contains four such formula units, which means that packing. In silicate and oxide structures the packing of
it has the composition of Cu4Fe4S8. Because this second oxygen is generally without omissions (that is, without
formula contains a common factor of 4, it is normally open spaces in the oxygen packing), so that the number of
divided by the factor resulting in CuFeS2. In either case, the oxygen ions (or atoms) per unit cell of a feldspar is a
ratio of all metal ions to sulfur is constant in both notations constant. This number turns out to be 32 oxygens, for
(8⬊8 or 2⬊2, both of which represent 1⬊1). The chemical four formula units of alkali feldspar, (Na,K)4Al4Si12O32,
formula states “There is one Cu ion, one Fe ion, and two per unit cell. Because of the common factor of 4 in
sulfur ions per formula.” We know what each of these ions this formulation, the formula is normally written as
(or atoms) weighs from its atomic weight. Copper is by far (Na,K)AlSi3O8, with the number of oxygens, eight, being
the heaviest with an atomic weight of 63.54; iron is some- a constant in the structure. In any recalculation sequence,
what lighter with an atomic weight of 55.85; and sulfur is by we must know to how many oxygens (as in silicates or
far the lightest with an atomic weight of 32.08. Because the oxides) or sulfurs (as in sulfides) the final formula must
formula states that there is one Cu, one Fe, and two S, we refer. For feldspar the number is eight oxygens.
can now calculate the relative weight contributions for these We will now go through the various steps that are neces-
various ions (or atoms). sary to convert the chemical analysis of an alkali feldspar to
its formula; see Table 5.1. Column 1, in Table 5.1, lists the
one Cu weighs 63.55 oxide components; column 2 lists the weight percentages
one Fe weighs 55.85 of the oxides. If we wish to know how may “molecules” of
and two S weigh 64.12 (that is, 2 ⫻ 32.06) oxide this represents for each of the weight percent values,
Total weight 183.52 we need to divide the values in column 2 by the appropri-
ate molecular weight (listed in column 3). (The word
The relative weight of any of the atoms, as referred to the molecule is put in quotation marks because most inorganic
total weight, is derived as follows: structures do not contain identifiable molecular groupings;
they are instead continuous packings or networks of atoms
63.55 or ions.) The division of the oxide weight percent value
Cu contributes ⫻ 100% ⫽ 34.62% in weight (column 2) by the appropriate molecular weight (column 3)
183.52
leads to a listing of relative numbers of “oxide molecules”
55.85
Fe contributes ⫻ 100% ⫽ 30.43% in weight (column 4: molecular proportions). Before proceeding fur-
183.52 ther, let us inspect the formulas of the oxide components in
64.12 column 1. SiO2 contributes one Si and two O per formula
S contributes ⫻ 100% ⫽ 34.94% in weight
183.52 or per molecule of SiO2; Al2O3 contributes two Al and
three O per formula or per molecule of Al2O3; all the
These calculated weight percentage values compare remaining oxide components (CaO, Na2O, and K2O) con-
closely to the numbers listed in analysis 3. This short cal- tribute each only one oxygen per formula or per molecule;
culation should give you a better understanding of the however, CaO contributes only one Ca, whereas Na2O and
earlier statement “A chemical analysis lists the relative K2O each contribute two metal ions. In advancing our con-
weight percentages of elements or oxides.” version further, we must ask how many metals and how
Let us now inspect analysis 4, that of an alkali feldspar. many oxygens does each of the “oxide molecules,” as
This is a typical example of the listing of oxide compo- recorded in column 4, contribute to the overall chemistry
nents in a silicate. The order, in going from top to of the alkali feldspar? We just determined these numbers by
bottom, is fairly standard with the oxides arranged in inspection of column 1, and indeed these numbers become
order of increasing radius of the metal ion (Si4⫹ being the multipliers in going from column 4 to columns 5 and 6,
smallest with a radius of 0.26 Å, and K⫹ the largest with a respectively. Column 5, labeled “cation proportions,”
radius of 1.51 Å). An inspection of such a listing of oxides records the number of metals contributed by each oxide
and their weight percentages informs the reader of compound. Column 6, labeled “number of oxygens,”
the major elements (Si, Al, Ca, Na, K, and O) that must records the number of oxygens contributed by each “mol-
be part of the chemical formula, but it gives absolutely ecule.” These oxygens will total to some number, 2.9889 in
no direct insight into metal ratios (or subscripts to the this case. This number is not meaningful in itself, but
elements) in the chemical formula. Various steps in the you must remember that this is the total of all the relative
 58 EXERCISE 5
TABLE 5.1 Example of the Recalculation of an Alkali Feldspar Analysis
1 2 3 4 5 6 7
Oxide Weight Molecular Molecular Cation Number of Number of Cations
Components Percentages Weights a Proportions Proportions Oxygens per Eight Oxygens

SiO2
Al2O3
65.67
20.84
60.08
101.96b
1.0930
0.2044
1.0930
0.4088
2.1860
0.6132
2.925
1.094 } 4.02 ⬇ 4.0

}
CaO 0.50 56.08 0.0089 0.0089 0.0089 0.024
Na2O 7.59 61.98 0.1225 0.2450 0.1225 0.655 0.99 ⬇ 1.0
K2O 5.49 94.20 0.0583 0.1166 0.0583 0.312
Total ⫽ 100.09 Total oxygens ⫽ 2.9889
8
Oxygen Factor: ⫽ 2.67656
2.9889
Final alkali feldspar formula: ( Na,K,Ca)1 (Al,Si)4O8

}
}
M site T site

a
Molecular weights given in Table 3.2, Manual of Mineral Science, 23rd ed.
b
Example of calculation of molecular weight of, e.g., Al2O3: atomic weight Al ⫽ 26.98; atomic weight O ⫽ 16;
two Al weigh 53.96; three O weigh 48; totaling 101.96.
 DERIVATION OF THE CHEMICAL FORMULA OF A MINERAL FROM ITS CHEMICAL ANALYSIS 59

oxygens contributed by the various “molecules.” Earlier, we M1 normally houses: all Al3⫹ that is “left over” after the
noted that structural analysis gave us the number 8 for the Si (tetrahedral) position has been filled to a total of 2.00
total number of oxygens per formula of feldspar. We can (see column 7, Table 5.2); all Fe3⫹; all Fe2⫹; all Mn2⫹; and
use this number 8 (for oxygen) by dividing the total value all Mg2⫹ (these ions represent a size range from 0.39 Å
of 2.9889 into 8, providing us with a multiplier, or oxygen for Al3⫹ to 0.83 Å for Mn2⫹; see table of ionic radii,
ratio, of 2.67656. We multiply the cation contributions Table 3.8, Manual of Mineral Science, 23rd ed., p. 49.
(values in column 5) by this factor to put the metal content The total of these “intermediate”-sized cations is 1.037,
of the analysis on the basis of eight oxygens. This gives us, very close to 1.0 as the structural formula requires (with
in column 7, the number of metal ions of each kind on the M1 completely filled). As noted earlier, the larger cations
basis of eight oxygens. (those with the Ca2⫹ size of 1.12 Å or larger) are housed
In alkali feldspar the number of silicons (in column 7) in the M2 site. Indeed, in column 7 of Table 5.2 their
will be considerably less than 4, generally close to 3.0 with total is 0.934, which is close to the ideal of 1.0. If one were
Al substituting for Si in the tetrahedral framework (the interested in making the ionic allocations for M1 and M2
T sites of the structure). Indeed Si ⫹ Al totals to 4.0, as is in column 7 even closer to the ideal 1 for both, one might
to be expected for a framework silicate structure with allocate all the Mn (0.027 cations) to the M2 site, it being
(Si ⫹ Al) : O ⫽ 4 : 8. The total for the remaining cations the largest of the intermediate cations that can commonly
amounts to approximately 1, with Na, K, and Ca substi- be found somewhat preferentially concentrated in the M2
tuting for one another in the one metal (M ) site of the site. With Mn so reallocated, the final site occupancy
feldspar structure. totals become M1 ⫽ 1.037 ⫺ 0.027 ⫽ 1.010 and M2 ⫽
This stepwise conversion should suffice as a preamble to 0.934 ⫹ 0.027 ⫽ 0.961; when both these numbers are
an assignment on the recalculation of pyroxene analyses. rounded off, they are very close to 1.0 each. Deviations
However, it may be helpful to inspect the various steps that from “ideality” are generally (but not always) the result of
you must complete in a pyroxene recalculation by studying analytical error; if they are not due to analytical error,
Table 5.2, which gives an example of a pyroxene analysis. they may represent cation omissions (if totals are low) or
Every column in this table is arrived at in a manner iden- interstitial additions (if totals are high).
tical to that for the feldspar recalculation, except for the The final structural formula for the clinopyroxene
difference in the oxygen factor. The clinopyroxene for- known as hedenbergite is given at the bottom of Table 5.2.
mula (that is, that of a monoclinic pyroxene) is based on six Quite independent of the complete formula recalcula-
oxygens per formula. For example, the simplest diopside tion schemes that we have presented, a question commonly
formula is CaMgSi2O6. The formula for the clinopyroxene asked is “What are the relative molecular percentages of
in Table 5.2 is not so simple because various elements sub- the major cations in a mineral?” In a mineral such as
stitute for each other in the various sites (M1, M2, and T ) a pyroxene, such a question commonly relates to the com-
of the clinopyroxene structure. This is the reason for a ponents FeO, MgO, and CaO (in molecular percentages)
somewhat more involved cation allocation scheme in col- or the equivalent values for Fe2⫹, Ca, and Mg (in atomic
umn 7 of Table 5.2 than there is in the equivalent column percentages). Now that we have recalculated the formula,
of Table 5.1. Please refer to Fig. 5.1 for a two-dimensional we can obtain the Fe2⫹ cation contribution of 0.767 (notice
projection on (001) of the clinopyroxene structure. The that we distinguish between Fe2⫹ and Fe3⫹ contributions);
smallest cation sites are those of tetrahedral coordination the Mg cation contribution is 0.131; the Ca cation contri-
(T ) with oxygen; these house Si4⫹ and Al3⫹. The other two bution is 0.899. Together these three cations total 1.797.
cation sites are marked as M1 and M2. The M1 is the The relative contributions of these three cations, expressed
smaller of the two, with the cations in this site housed in in percentages, can be obtained by dividing each value by
regular octahedral coordination with respect to the sur- the total and multiplying by 100%. The results of such
rounding oxygens. The coordination of the M2 site is calculations are shown in column 8 of Table 5.2.
more variable, ranging from 6-fold (octahedral) to 8-fold Identical results for the relative percentages of the molec-
(toward cubic configuration, but generally somewhat ular contributions of FeO, MgO, and CaO can be obtained
irregular in geometry) depending on the overall size of the very quickly without completing the whole formula recalcu-
cations occupying this M2 site. In clinopyroxenes the M2 lation. We can take from column 4 (Table 5.2) the values for
site is definitely 8-fold in coordination (as such not regular the molecular proportions of FeO (⫽0.310), for MgO
and not octahedral) with the larger cations of the structure (0.053), and for CaO (⫽0.363). If we total these three val-
(Ca2⫹, Na⫹, and K⫹) occupying this site. If, on the other ues, we can obtain the relative percentage contributions of
hand, as in orthopyroxenes (orthrohombic pyroxenes) these three oxide “molecules” by a calculation analogous to
smaller cations such as Fe2⫹ and Mg2⫹ are housed in the that given in Column 8. This is shown in column 9 of Table
M2 site, the coordination polyhedron of M2 becomes more 5.2. Indeed, the values obtained are identical to those in col-
regularly octahedral. As a result of the size restrictions umn 8; minor variations in the decimal places are due to
on the M1 and M2 structural sites in clinopyroxenes, the rounding in the various steps toward column 7. This illus-
following generalization can be made. trates that relative molecular percentages can be obtained
 60 EXERCISE 5
TABLE 5.2 Example of the Recalculation of a Clinopyroxene (Hedenbergite) Analysis.
1 2 3 4 5 6 7 8 9
Oxide Weight Molecular Molecular Cation Number of Number of Cations Atomic Proportions
Components Percentages Weights Proportions Proportions Oxygens per Six Oxygens of Fe2⫹, Mg and Ca From Column 4

SiO2 48.00 60.08 0.799 0.799 1.598 1.978

} 2.00 Fe2⫹ ⫽ 0.767 Molecular proportions of:

}
0.022
Al2O3 0.63 101.96 0.006 0.012 0.018 0.030 Mg ⫽ 0.131 FeO ⫽ 0.310
0.008
Fe2O3 3.32 159.70 0.021 0.042 0.063 0.104 Ca ⫽ 0.899 MgO ⫽ 0.053
FeO 22.85 71.85 0.310 0.310 0.310 0.767 1.037 Total ⫽ 1.797 CaO ⫽ 0.363
MnO 0.81 70.94 0.011 0.011 0.011 0.027 0.767 Total ⫽ 0.726
Fe 2⫹ ⫽ ⫻ 100%
MgO 2.12 40.30 0.053 0.053 0.053 0.131 1.797
Relative percentage

}
CaO 20.35 56.08 0.363 0.363 0.363 0.899 ⫽ 42.68% contributions:

Na2O 0.34 61.98 0.005 0.010 0.005 0.025 0.934 0.131 0.310
Mg ⫽ ⫻ 100% FeO ⫽ ⫻ 100%
1.797 0.726
K2O 0.18 94.20 0.002 0.004 0.002 0.010
⫽ 7.29% ⫽ 42.69%
Total 98.00 a
Total oxygens ⫽ 2.423
0.899 0.053
6 Ca ⫽ ⫻ 100% MgO ⫽ ⫻ 100%
Oxygen factor: ⫽ 2.476 1.797 0.726
2.423
⫽ 50.02% ⫽ 7.30
Total 99.99% 0.363
CaO ⫽ ⫻ 100%
0.726
Structural formula: (Ca,Na,K)0.9 (Al,Fe3⫹,Fe2⫹, Mn,Mg)1.0(Si,Al)2.0O6
⫽ 50.00%

冦 }
}

}
M2 M1 T

Analysis contains 1.72 H2O, with overall total of 99.72.

a
 DERIVATION OF THE CHEMICAL FORMULA OF A MINERAL FROM ITS CHEMICAL ANALYSIS 61

with very few conversions; indeed, a complete mineral for- you with the data to write a proper augite formula with
mula recalculation is unnecessary. Because we already had cations assigned to the T, M1, and M2 sites. Write this
obtained the pyroxene formula, however, we had access to structural formula below the columns, at the bottom of
the numbers in column 7. the page in Table 5.3, and identify which cations you
group together in which site. In column 8 you are asked
MATERIALS for the atomic proportions of Fe2⫹, Mg, and Ca. This you
obtain from the numbers in column 7. You are asked to do
Chemical analyses given for two different pyroxenes, in
a similar calculation for the molecular proportions of
Tables 5.3 and 5.4, respectively. An electronic calculator is
FeO, MgO, and CaO (in column 9) as determined from
essential, and you must consult a tabulation of atomic
the molecular proportions in column 4.
weights (e.g., Table 3.2 in Manual of Mineral Science,
23rd ed.) so that you can compute the appropriate molec- 2. The analysis in Table 5.4 also shows a small amount of
ular weights. TiO2. In the assignment of cations allocate this to the M1
site. The recalculation scheme in this table must be based
on three oxygens because the formulas of members of the
orthopyroxene series are most generally reported in the
ASSIGNMENT
form of MgSiO3 to FeSiO3. All the various recalculation
Given the chemical analyses for augite (a monoclinic steps are analogous to those you performed in Table 5.3
pyroxene) and hypersthene (a member of the orthorhom- or were shown in the example of Table 5.2. When you
bic pyroxenes, or orthopyroxenes) in Tables 5.3 and 5.4, reach column 7, be careful in your assignment of cations
respectively, complete the various formula recalculation to the M1 and M2 sites. In an orthopyroxene, the M2 is
steps. The column headings are the same as those in the essentially octahedral and as such is smaller than the M2
example calculation in Table 5.2. site in a clinopyroxene. The small amounts of Ca, Na, K,
and Mn and a large proportion of Fe2⫹ can be assigned to
1. In Table 5.3 the weight percentage analysis shows M2 in orthopyroxene because the M2 site is still somewhat
some TiO2. In the assignment of cations to structural sites larger than the M1 site. Record your final structural for-
(column 7, and the structural formula), this is normally mula at the bottom of the table and clearly mark which
grouped with Fe2⫹, Mg, Mn, and Fe3⫹ in the M1 site. The cations you have grouped in which structural sites.
recalculation scheme must be based on six oxygens in the Columns 8 and 9 request that you obtain atomic percent-
augite formula. The oxygen factor therefore is 6 divided ages of Fe, Mg, and Ca, and molecular percentages of
by the total for the number of oxygens obtained in FeO, MgO, and CaO, respectively.
column 6. The number of cations in column 7 provides
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 Assignment on the Recalculation of the Chemical Analysis of an Augite.
Copyright John Wiley & Sons, Inc.

TABLE 5.3

EXERCISE 5
1 2 3 4 5 6 7 8 9
Oxide Weight Molecular Molecular Cation Number of Number of Cations Atomic Proportions of Molecular Proportions
Components Percentages Weights Proportions Proportions Oxygens per Six Oxygens Fe2ⴙ, Mg, and Ca of FeO, MgO, CaO

SiO2 48.11

TiO2 1.14

Al2O3 7.26

Fe2O3 3.13

FeO 4.86

MnO 0.11

MgO 14.04

CaO 20.46

Na2O 0.66

K2O 0.04

Student Name
Total 99.81

Structural formula ________________________________________

(Indicate what cations are assigned to which sites in the structure.)

63
This page intentionally left blank
 Assignment on the Recalculation of the Chemical Analysis of a member of the orthopyroxene series.
Copyright John Wiley & Sons, Inc.

TABLE 5.4

EXERCISE 5
1 2 3 4 5 6 7 8 9
Oxide Weight Molecular Molecular Cation Number of Number of Cations Atomic Proportions of Molecular Proportions
Components Percentages Weights Proportions Proportions Oxygens per Three Oxygens Fe2ⴙ, Mg, and Ca of FeO, MgO, CaO

SiO2 50.26

TiO2 0.16

Al2O3 3.13

Fe2O3 0.65

FeO 26.54

MnO 0.76

MgO 16.36

CaO 1.76

Na2O 0.24

K2O 0.13

Student Name
Total 99.99

Structural formula ________________________________________

(Indicate what cations are assigned to which sites in the structure.)

65