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Let's consider the composition $\ce{Hg_{0.7}Cd_{0.3}Te}$ which appears in my data.

As I remember from my chemical knowledge it's not possible having non-integers numbers as coefficients of elements. Moreover, this is clearly not the percentage representation, since we have $1$ atom of tellurium. So is this some sort of reduced chemical formula that should be multiplied by a smallest suitable integer to get an appropriate result? If not, what does this exactly represent?

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4 Answers 4

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The rule that coefficients have to be integers applies to compounds containing discrete molecules, but some classes of compounds don't

There is an important rule in chemistry that the formulae of molecules must contain integer ratios of elements. But not every substance in the (very broad) field of chemistry is made of discrete molecules.

There are at least two major exceptions where the units don't contain discrete molecules: many minerals and metal alloys.

Metals don't consist of molecules. They are more like a sea of ions in a soup of free electrons. And many metals can freely mix in any ratio (though in many cases it is even more complicated and some alloys consist of a fine-grained mix of multiple alloys of different composition). But for the simpler cases virtually any ratio of several metals is possible (think of this as being like a solution of both salt and sugar dissolved in water: a wide variety of ratios of sugar and salt are possible).

This appears to be the case that prompted the question. Many metal alloys are, in effect, solid solutions of one or more metals in another metal and any ratio of the components is possible.

Another class where non-integer ratios are common is minerals. Many consist of a variety of continuous chains of silicate (Silicon-oxygen) structures making up sheets, chains or other complex structures. These have a net negative charge which is balanced in the mineral by a variety of different metal ions. But, because any metal with the right charge and size can do that job, they often consist of non-integer ratios of metals.

So, for some classes of substance where the building blocks are not discrete molecules, non-integer ratios of components are perfectly possible.

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    $\begingroup$ I support the Matt's answer, well written. The third major exception ( aside of allloys and minerals) are synthetic ceramic or semiconductor materials. $\endgroup$
    – Poutnik
    Commented Feb 21, 2022 at 14:06
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Formulas with non-stoichiometric rational number coefficients do not represent molecular structures, but just empirical molar ratio of involved elements. For solid matter, unless it is composed from molecules, even formulas with small integer coefficients do not represent molecular structure, but are expressions of element molar ratios.

E.g. $\ce{CaF2}$ does not mean the respective mineral is composed from $\ce{CaF2}$ molecules, but it means the ratio of $\ce{Ca^2+}$ and $\ce{F-}$ ions is in the ratio 1 : 2.

Some natural or man-made compounds or materials do not have element ratios in small integer numbers, so their formulas use rational numbers. Formally, any multiple of given ratio can be used, but practically at least one coefficient is normalized to integer number. For cases 2 elements are interchangeable in composition, their coefficients often represent their mutual molar fraction, or its integer multiple. In other cases, there is taken an ideal formula as a template and non-integer coefficients express deviation from it.

For your case of $\ce{Hg_{0.7}Cd_{0.3}Te}$, the mixed cadmium/mercury telluride has both metals mutually interchangable with molar fraction coefficients. Note that they may not be quite nice and round 0.7 or 0.3, but generally any rational number between 0 and 1.

Take it as a particular formula for the general empirical formula $\ce{Hg_{x}Cd_{1-x}Te}$, $x \le 1$, $x \ge 0$.

For $x=0$, it is $\ce{CdTe}$, for $x=1$, it is $\ce{HgTe}$.

It is quite common form for formula notation of mixed chalkogenides where the coefficients are not stoichiometric.

Typical cases are metal oxides with more than 1 oxidation states, where coefficients are empirical. $\ce{FeO}$ is rather $\ce{Fe_{0.9x}O}$ as there is, aside of $\ce{Fe^{II}}$, also $\ce{Fe^{III}}$. The general formula could be $$\ce{Fe^{II}_{1-x}Fe^{III}_{x}O_{1+0.5x}}$$ or $$\ce{Fe^{II}_{\frac{1-x}{1+0.5x}}Fe^{III}_{\frac{x}{1+0.5x}}O}$$.

It could be formally written as $\ce{a FeO . b Fe2O3}$, but such a notation does not bring any advantage, as it does not represent any real molecular structure.

$\ce{Fe2O3}$ does not represent any real molecular structure either. It just happens that the molar ratio of elements is in this (idealized) case expressed in small integer numbers.

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  • $\begingroup$ many thanks for your answer. Anyway, could you elaborate a bit more on that? I mean, I still don't understand what is the meaning of considering 0.7 atoms of Hg.. $\endgroup$ Commented Feb 21, 2022 at 11:39
  • $\begingroup$ So here we have exactly $1$ atom of $O$ (constant) and I guess (in light of what you said before) that this chemical formula might be seen as $Fe_xO$ but I don't see specific constrains for the $x$ here. I'm sorry but I haven't any experience in Chemistry/Materials Science $\endgroup$ Commented Feb 21, 2022 at 11:49
  • $\begingroup$ You may be too focused on an idea of a molecule, where there must be integer atom numbers. Consider it as the molar fractions of metals in the $\ce{MTe}$. What alternative formula would you suggest for $\ce{Fe_{0.9678 \pm 0.0002}O}$? $\endgroup$
    – Poutnik
    Commented Feb 21, 2022 at 11:49
  • $\begingroup$ Exactly 1 O atom means nothing here. The formula expresses empirical ratio between atom counts, with deliberate conventional choice of a small integer for one element. For mixed substances, the formula is conventionally kept in the form of pure forms, with fractional coefficients. $\endgroup$
    – Poutnik
    Commented Feb 21, 2022 at 11:55
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    $\begingroup$ None, really. this is the best one. $\endgroup$
    – Poutnik
    Commented Feb 21, 2022 at 12:07
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Maurice's answer is correct, but let me try to explain my own way.

The fractional coefficients aren't just picked out of a hat: they add up to 1. That's not an accident! The point is that this is a solid solution with Te2- ions and X2+ ions, where X is Hg2+ or Cd2+, potentially occupying the same position in the crystal lattice. You could have a 69% and 31%, or 71% and 29%, and it would work just as well. Converting the percentages to integers would be misleading, because it would give the impression that they are, or should be, exact proportions, which have to be maintained to avoid some fundamental change in structure. Also, using the fractional coefficients typically makes it quite clear who has to match up with who to fill up a specific position in the lattice together.

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    $\begingroup$ It may be "correct", but it is irrelevant to the question which is not about this specific compound but about fractions in formulae in general. $\endgroup$
    – matt_black
    Commented Feb 22, 2022 at 9:16
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    $\begingroup$ They don't always add up to 1 though; suboxides might be writte as integer metal, fractional oxygen. $\endgroup$
    – Jan
    Commented Feb 22, 2022 at 14:16
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The formula $\ce{Hg_{0.7}Cd_{0.3}Te}$ means that $\ce{Hg}$ and $\ce{Cd}$ have the same dimension, nearly same radius, and same valence. They can be interchanged, in any proportion between $0$ to $100$%. Here there are $70$% mercury and $30$% cadmium. But it could also have been possible to get any other coefficient $x$ for mercury ($x<1$}, provided the coefficient of cadmium is $(1 - x)$.

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    $\begingroup$ The formula doesn't mean that: it simply describes the relative atomic composition. And you have miscalculated the proportions for the whole compounds as you ignored the proportion of Te. $\endgroup$
    – matt_black
    Commented Feb 21, 2022 at 17:33
  • $\begingroup$ Les coefficients $0.7$ and $0.3$ are not depending on the proportion of $\ce{Te}$. For each Te atom, there is $x$ atom $\ce{Hg}$ and ${1-x}$ atom Cd $\endgroup$
    – Maurice
    Commented Feb 21, 2022 at 19:35
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    $\begingroup$ But what people want to know for an alloy is the atomic proportions of the whole alloy, not just the proportion of the ingredients other than the commonest one. Eg the whole alloy has 35% Hg not 70%. Nothing in the formula says that a version of this alloy couldn't have more Hg than Te, just that this version of the alloy doesn't. $\endgroup$
    – matt_black
    Commented Feb 21, 2022 at 19:44
  • $\begingroup$ @matt_black. Who tells you it's an alloy ? It may be a compound like $\ce{ZnS}$ where $\ce{Zn}$ has been replaced partly by $\ce{Cd}$ (30%) and partly by $\ce{Hg}$ (70%), which are all in the same 12th column. And where the sulfur $\ce{S}$ atom is replaced by $\ce{Te}$, which is also in the same 16th column. $\endgroup$
    – Maurice
    Commented Feb 21, 2022 at 22:18
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    $\begingroup$ @Maurice The disagreement between us may arise because you are providing an answer based on this specific compound not one based on the question which is about how fractions arise in chemical formulae in general. Nothing in the formula says alloy but alloys are a common example of where such formulae arise. Any specific knowledge of this compound is not relevant to the general answer and adding it is confusing. $\endgroup$
    – matt_black
    Commented Feb 22, 2022 at 9:12

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