Polyatomic ions

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In this article, we will discuss polyatomic ions. The prefix poly- means
many, so a polyatomic ion is an ion that contains more than one atom.
This differentiates polyatomic ions from monatomic ions, which contain
only one atom. Examples of monatomic ions include \text{Na}^+Na+start
text, N, a, end text, start superscript, plus, end
superscript, \text{Fe}^{3+}Fe3+start text, F, e, end text, start superscript,
3, plus, end superscript, \text{Cl}^-Cl−start text, C, l, end text, start
superscript, minus, end superscript, and many, many others. This article
assumes you have a knowledge of basic monatomic ions as well as the
conventions for naming ionic compounds and writing their chemical
formulas.

For a review on these topics, see this article on monatomic ions and
naming ionic compounds.
Polyatomic ions are everywhere! Chalk is made up of calcium carbonate, \text{CaCO}_3CaCO3start text, C,
a, C, O, end text, start subscript, 3, end subscript, which contains calcium cations, \text{Ca}^{2+}Ca2+start
text, C, a, end text, start superscript, 2, plus, end superscript, and carbonate anions, \text{CO}_3^{2-}CO32−
start text, C, O, end text, start subscript, 3, end subscript, start superscript, 2, minus, end superscript, which
are polyatomic ions. Image credit: Alice on Flickr, CC BY-NC-ND 2.0

Structure of polyatomic ions

We can think about polyatomic ions by comparing them to monatomic
ions. A monatomic ion is an atom that has been ionized by gaining or
losing electrons. The ion has a net charge because the total number of
electrons is not balanced by the total number of protons in the nucleus.
Thus, compared to the neutral atom, we have extra electrons—in the
case of a negatively charged anion—or not enough electrons—in the case
of a positively charged cation. For example, a neutral chlorine atom has
an atomic number of 17, which means it has 17 protons and 17 electrons.
The neutral atom will sometimes gain an extra electron to become the
chloride anion, \text{Cl}^-Cl−start text, C, l, end text, start superscript,
minus, end superscript:
~~~~~~~~~~~~~\blueD{\text{Cl}}~~~+~~~e^-
~~~\rightarrow~~~ \purpleC{\text{Cl}^-
} Cl + e− → Cl−space, space, space, space, space, space,
space, space, space, space, space, space, space, start color #11accd, start
text, C, l, end text, end color #11accd, space, space, space, plus, space,
space, space, e, start superscript, minus, end superscript, space, space,
space, right arrow, space, space, space, start color #aa87ff, start text, C, l,
end text, start superscript, minus, end superscript, end color #aa87ff

~~~~\blueD{17\,\text{electrons}}~~~~~~~~~~~~~~\purpleC{18\,\text{elect
rons}} 17electrons 18electronsspace, space, space, space, start
color #11accd, 17, start text, e, l, e, c, t, r, o, n, s, end text, end color
#11accd, space, space, space, space, space, space, space, space, space,
space, space, space, space, space, start color #aa87ff, 18, start text, e, l, e,
c, t, r, o, n, s, end text, end color #aa87ff
~~~~~17\,\text{protons}~~~~~~~~~~~~~~~~17\,\text{protons} 17protons
17protonsspace, space, space, space, space, 17, start text, p, r, o,
t, o, n, s, end text, space, space, space, space, space, space, space, space,
space, space, space, space, space, space, space, space, 17, start text, p, r, o,
t, o, n, s, end text

After gaining an electron, the chloride anion has 17 protons and 18

electrons. Since there is one extra electron compared to the number of
protons, the ion has a net charge of 1-.

Similarly, we can think of a polyatomic ion as a molecule that has been

ionized by gaining or losing electrons. In a polyatomic ion, the group of
covalently bonded atoms carries a net charge because the total number
of electrons in the molecule is not equal to the total number of protons in
the molecule. When drawing Lewis dot structures, the overall charge on
a polyatomic ion is equal to the sum of the formal charges on each atom
in the ion.
[What is formal charge?]

Lewis structure of hydroxide.

The Lewis dot structure for the hydroxide ion. Dots around \text{O}Ostart text, O, end text indicate three
lone pairs, and the line between \text{H}Hstart text, H, end text and \text{O}Ostart text, O, end
text represents a covalent bond containing two shared electrons. The overall charge on the polyatomic ion
is 1-, which is indicated to the upper right outside the brackets. Image credit: Wikimedia Commons, CC BY-
SA 3.0

For example, let's consider the polyatomic ion \text{OH}^-OH−start text,

O, H, end text, start superscript, minus, end superscript, which is known
as hydroxide. On the left we see the dot structure of the hydroxide ion. It
contains one oxygen atom and one hydrogen atom. The single line
between them represents the covalent bond, which contains two
electrons shared between \text{H}Hstart text, H, end
text and \text{O}Ostart text, O, end text. The dots around \text{O}Ostart
text, O, end text represent lone pairs of electrons. In hydroxide, the
oxygen has three lone pairs of electrons, which makes for six lone pair
electrons in total.

The net charge on the hydroxide ion is indicated by putting the entire dot
structure inside square brackets with the charge on the upper right. We
see that hydroxide has a 1- charge, which means the ion has one more
electron than there are protons in the nuclei of a hydrogen atom plus an
oxygen atom.

Concept check: How many protons and electrons are in a hydroxide

ion?
[Show the answer.]
Total # protons=protons in H+protons in
O=1proton+8protons=9protons

Common polyatomic ions

Polyatomic ions are everywhere! Bicarbonate ions, \text{HCO}_3^-
HCO3−start text, H, C, O, end text, start subscript, 3, end subscript, start
superscript, minus, end superscript, help maintain the pH level of our
blood, while phosphates, \text{PO}_4^{3-}PO43−start text, P, O, end text,
start subscript, 4, end subscript, start superscript, 3, minus, end
superscript, are extremely important in various metabolic processes.
Being familiar with the names, charges, and formulas of the most
common polyatomic ions will be helpful for recognizing ionic
compounds and predicting their reactivity. The following table lists some
of the common polyatomic ions.
\begin{array}{c c | c c} \textbf{Formula} & \textbf{Name} &
\textbf{Formula} & \textbf{Name}\\ \hline \text{Hg}_2^{2+}
& \text{Mercury(I)} & \text{SCN}^- & \text{Thiocyanate} \\
\text{NH}_4^+ & \text{Ammonium} & \text{CO}_3^{2-} &
\text{Carbonate} \\ \text{NO}_2^- & \text{Nitrite} &
\text{HCO}_3^- & \text{Hydrogen carbonate (bicarbonate*)} \\
\text{NO}_3^- & \text{Nitrate} & \text{ClO}^- &
\text{Hypochlorite} \\ \text{SO}_3^{2-} & \text{Sulfite} &
\text{ClO}_2^- & \text{Chlorite} \\ \text{SO}_4^{2-} &
\text{Sulfate} & \text{ClO}_3^- & \text{Chlorate} \\
\text{HSO}_4^- & \text{Hydrogen sulfate (bisulfate*)} &
\text{ClO}_4^- & \text{Perchlorate} \\ \text{OH}^- &
\text{Hydroxide} & \text{C}_2\text{H}_3\text{O}_2^-(\text{or
CH}_3\text{COO}^{-})& \text{Acetate} \\ \text{CN}^- &
\text{Cyanide} & \text{MnO}_4^- & \text{Permanganate} \\
\text{PO}_4^{3-} & \text{Phosphate} &
\text{Cr}_2\text{O}_7^{2-} & \text{Dichromate} \\
\text{HPO}_4^{2-} & \text{Hydrogen phosphate} &
\text{CrO}_4^{2-} & \text{Chromate} \\
\text{H}_2\text{PO}_4^- & \text{Dihydrogen phosphate} &
\text{O}_2^{2-} & \text{Peroxide} \\ & &
\text{C}_2\text{O}_4^{2-} & \text{Oxalate}
\end{array}FormulaHg22+NH4+NO2−NO3−SO32−SO42−HSO4−
 OH−CN−PO43−HPO42−H2PO4−
NameMercury(I)AmmoniumNitriteNitrateSulfiteSulfateHydrog
en sulfate (bisulfate*)HydroxideCyanidePhosphateHydrogen ph
osphateDihydrogen phosphateFormulaSCN−CO32−HCO3−
ClO−ClO2−ClO3−ClO4−C2H3O2−(or CH3COO−)MnO4−Cr2O72−
CrO42−O22−C2O42−
NameThiocyanateCarbonateHydrogen carbonate (bicarbonate*)
HypochloriteChloriteChloratePerchlorateAcetatePermanganateD
ichromateChromatePeroxideOxalate
* An informal but commonly used name.

We will be referring to the polyatomic ions in this table for the

remainder of the article!
[How can I remember SO MANY ions?!]

Names and chemical formulas of compounds

containing polyatomic ions
You can probably find polyatomic ions in your kitchen! Baking soda is a common name for sodium
bicarbonate, \text{NaHCO}_3NaHCO3start text, N, a, H, C, O, end text, start subscript, 3, end subscript,
which contains the bicarbonate ion \text{HCO}_3^-HCO3−start text, H, C, O, end text, start subscript, 3, end
subscript, start superscript, minus, end superscript. Image credit: pixabay, CC0 1.0

Now that we have a reference for many of the common polyatomic ions,
let's look at how to name and write the chemical formulas for
compounds that contain them. There are two main things to keep in
mind:

1. If a compound contains more than one polyatomic ion of the same type,
we need to place parentheses around the ion's formula before using a
subscript to indicate how many ions of that type are in the compound.
2. The overall charge for the ionic compound must be neutral, which means
the sum of the charges from the cations and anions should add up to
zero. We can use this rule to figure out the formula of an ionic compound
when we know the charge on the anion and the cation. This rule can also
be useful for deducing the charge of an ion when the chemical formula
for the ionic compound is known.

Let's consider some examples.

Example 1: Finding the chemical formula

from the compound name
What is the chemical formula for calcium hydroxide?

Calcium is an alkaline earth metal—Group 2 on the periodic table—so it

forms ions with a 2+ charge. From our table, we know that hydroxide has
the formula \text{OH}^-OH−start text, O, H, end text, start superscript,
minus, end superscript and that it carries a 1- charge. We will need two
hydroxide ions to exactly cancel the 2+ charge
on \text{Ca}^{2+}Ca2+start text, C, a, end text, start superscript, 2, plus,
end superscript. When writing out the formula, we include parentheses
around \text{OH}OHstart text, O, H, end text followed by a subscript of 2,
to make it clear that there are two hydroxide ions for
every \text{Ca}^{2+}Ca2+start text, C, a, end text, start superscript, 2,
plus, end superscript cation. Thus, the chemical formula for the compound
is \text{Ca(OH)}_2Ca(OH)2start text, C, a, left parenthesis, O, H, right
parenthesis, end text, start subscript, 2, end subscript.
Concept check: Why would \text{CaOH}_2CaOH2start text, C, a, O, H,
end text, start subscript, 2, end subscript be the incorrect formula
for calcium hydroxide?
[Show the answer.]

\text{CaOH}_2start text, C, a, O, H, end text, start subscript, 2, end

subscript\text{O}start text, O, end text\text{H}start text, H, end
text\text{OH}^-start text, O, H, end text, start superscript, minus, end
superscript-minus

Example 2: Naming ionic compounds that

contain polyatomic ions
What is the name of the compound with the
formula \text{Ni}_3(\text{PO}_4)_2Ni3(PO4)2start text, N, i, end text,
start subscript, 3, end subscript, left parenthesis, start text, P, O, end
text, start subscript, 4, end subscript, right parenthesis, start
subscript, 2, end subscript?

When naming ionic compounds, it helps to first break down the formula
into the cation(s) and the anion(s). In this compound, the cation is based
on nickel. Nickel is a transition metal that can form multiple kinds of
cations with different charges. That means we will need to figure out the
charge on the nickel ion in this specific compound so that we can specify
it when naming the ionic compound! Luckily, we know the charge on the
anion: phosphate is a polyatomic ion that always has a charge of 3-. Since
the overall charge for an ionic compound is zero, we can use the
chemical formula and the charge on phosphate to calculate the charge on
the nickel ion:
Net charge=0=(# cations×cation charge)+(# anions×anion
charge)
If we rearrange this equation, we see that the sum of the charges from
the cations must be equal to -1−1minus, 1 times the sum of the charges
from the anions.

# cations×cation charge=−1×(# anions×anion charge)

We can plug in the known values for the number of cations and anions—
from the chemical formula—and the anion charge, then solve for the
charge on nickel:
\begin{aligned}\text{3}\times\greenD{\text{cation
charge}}&=-1\times (\text{2}\times{3-})=6+ \\ \\
\greenD{\text{cation
charge}}&=\dfrac{6+}{3}=2+\end{aligned}3×cation chargecati
on charge=−1×(2×3−)=6+=36+=2+
Now we know the cation in our compound is nickel (II). To name the
whole compound, we start with the cation name with the charge
included in parentheses using Roman numerals, followed by the anion
name.

Therefore, the name of the compound is nickel (II) phosphate.

Example 3: Breaking apart an ionic

compound into ions
What are the constituent ions in the ionic
compound \text{Ca(MnO}_4)_2Ca(MnO4)2start text, C, a, left
parenthesis, M, n, O, end text, start subscript, 4, end subscript, right
parenthesis, start subscript, 2, end subscript?

Specify the formula, charge, and number of each ion.

When analyzing the formula of an ionic compound, we first look for the
formulas of familiar ions. In this case, we notice that \text{MnO}_4^-
MnO4−start text, M, n, O, end text, start subscript, 4, end subscript, start
superscript, minus, end superscript, permanganate, is one of the
polyatomic ions listed in our table above. In this compound, we see that
we have two ions of permanganate.
[How do you know there are two ions of permanganate?]

\text{MnO}_4start text, M, n, O, end text, start subscript, 4, end subscript

Because permanganate carries a 1- charge, this means it is contributing a

net charge of 2\times(12×(12, times, left parenthesis, 1-)=2−)=2minus,
right parenthesis, equals, 2-−minus to the ionic compound. Recall that in
all ionic compounds, the net charge of the compound must be zero.
Therefore, calcium must be present as the cation \text{Ca}^{2+}Ca2+start
text, C, a, end text, start superscript, 2, plus, end superscript in order to
balance out the 2- net charge from the two \text{MnO}_4^-MnO4−start
text, M, n, O, end text, start subscript, 4, end subscript, start superscript,
minus, end superscript ions.

To check our reasoning, we can ask ourselves, "Does calcium typically

form cations with a 2+ charge?" Because \text{Ca}Castart text, C, a, end
text is a Group 2 metal, it will typically lose two electrons to form 2+
cations. Thus our answer is consistent with our knowledge of chemical
reactivity, yay!

Therefore, the ionic compound \text{Ca(MnO}_4)_2Ca(MnO4)2start text,

C, a, left parenthesis, M, n, O, end text, start subscript, 4, end subscript,
right parenthesis, start subscript, 2, end subscript contains
one \text{Ca}^{2+}Ca2+start text, C, a, end text, start superscript, 2, plus,
end superscript cation and two \text{MnO}_4^-MnO4−start text, M, n, O,
end text, start subscript, 4, end subscript, start superscript, minus, end
superscript anions.

It is often useful to be able to break down an ionic compound into the

constituent ions. One example of such a situation is when an ionic
compound is dissolved in water for a reaction. Many ionic compounds
are water-soluble, and the constituent ions dissociate when in solution.
The dissociated ions can then go off and participate in their own
chemistry independently of the other ions in the original ionic
compound.

Conclusion
Just as ions are formed when neutral atoms gain or lose electrons, a
polyatomic ion is formed when a neutral molecule gains or loses
electrons. Therefore, a polyatomic ion is a group of covalently bonded
atoms that carries a net charge due to the fact that the total number of
electrons in the molecule is not equal to the total number of protons in
the molecule. In the Lewis dot structure of a polyatomic ion, the sum of
the formal charges on all the atoms must equal the net charge on the ion.

Being familiar with the most common polyatomic ions will be helpful for
recognizing ionic compounds and predicting their reactivity. While
learning all the polyatomic ions can seem daunting, there are patterns to
the formulas, names, and charges of many ions. These patterns can be
learned, so you don't have to simply memorize all the ions.
 Bonus: Once you know the polyatomic ions, you can play the game, "Find
the polyatomic ion," which involves looking for examples of compounds
that contain polyatomic ions in everyday life. We gave examples of
baking soda and chalk in this article. Can you find more? Hint: check out
the ingredients list of your lotion, shampoo, or toothpaste. Feel free to
post others in the comments below!
[Attributions and References]

1.

Try it!
Problem 1

What is the chemical formula for lithium hydrogen phosphate?

Choose 1 answer:
Choose 1 answer:

(Choice A)

\text{Li}_3\text{PO}_4Li3PO4start text, L, i, end text, start subscript, 3,

end subscript, start text, P, O, end text, start subscript, 4, end subscript

(Choice B)

\text{Li}_2\text{HPO}_4Li2HPO4start text, L, i, end text, start subscript,

2, end subscript, start text, H, P, O, end text, start subscript, 4, end
subscript

(Choice C)

C
 \text{LiHPO}_4LiHPO4start text, L, i, H, P, O, end text, start subscript, 4,
end subscript

(Choice D)

\text{LiH}_2\text{PO}_4LiH2PO4start text, L, i, H, end text, start

subscript, 2, end subscript, start text, P, O, end text, start subscript, 4, end
subscript
[Hint 1]

\text{Li}^+start text, L, i, end text, start superscript, plus, end

superscript\text{HPO}_4^{2-}start text, H, P, O, end text, start subscript,
4, end subscript, start superscript, 2, minus, end superscript
[Hint 2]

\text{HPO}_4^{2-}start text, H, P, O, end text, start subscript, 4, end

subscript, start superscript, 2, minus, end superscript\text{Li}^+start
text, L, i, end text, start superscript, plus, end superscript

\text{Li}_2\text{HPO}_4start text, L, i, end text, start subscript, 2, end

subscript, start text, H, P, O, end text, start subscript, 4, end subscript
Check

Problem 2

What is the name of the compound with the chemical

formula (\text{NH}_4)_2\text{S}(NH4)2Sleft parenthesis, start text, N,
H, end text, start subscript, 4, end subscript, right parenthesis, start
subscript, 2, end subscript, start text, S, end text ?
Choose 1 answer:
Choose 1 answer:

(Choice A)

A
 nitrogen bisulfide

(Choice B)

nitrogen hydrogen sulfide


(Choice C)

ammonium sulfide

(Choice D)

ammonium sulfate
[Hint 1]

\text{NH}_4^+start text, N, H, end text, start subscript, 4, end subscript,

start superscript, plus, end superscript\text{S}^{2-}start text, S, end text,
start superscript, 2, minus, end superscript
[Hint 2]

\text{NH}_4^+start text, N, H, end text, start subscript, 4, end subscript,

start superscript, plus, end superscript\text{S}^{2-}start text, S, end text,
start superscript, 2, minus, end superscript
Check

Problem 3

What are the constituent ions in the ionic

compound \text{FeCr}_2\text{O}_7FeCr2O7start text, F, e, C, r, end
text, start subscript, 2, end subscript, start text, O, end text, start
subscript, 7, end subscript?

Specify the formula, charge, and number of each ion.

Choose 1 answer:
 Choose 1 answer:

(Choice A)

1\text{ Fe}^+1 Fe+1, start text, space, F, e, end text, start superscript, plus,
end superscript cation and 1\text{ Cr}_2\text{O}_7^-1 Cr2O7−1, start text,
space, C, r, end text, start subscript, 2, end subscript, start text, O, end
text, start subscript, 7, end subscript, start superscript, minus, end
superscript anion

(Choice B)

1\text{ Fe}^{2+}1 Fe2+1, start text, space, F, e, end text, start superscript,
2, plus, end superscript cation and 1\text{ Cr}_2\text{O}_7^{2-}1 Cr2O72−
1, start text, space, C, r, end text, start subscript, 2, end subscript, start
text, O, end text, start subscript, 7, end subscript, start superscript, 2,
minus, end superscript anion

(Choice C)

1\text{ Fe}^{2+}1 Fe2+1, start text, space, F, e, end text, start superscript,
2, plus, end superscript cation, 2\text{ Cr}^{6+}2 Cr6+2, start text, space,
C, r, end text, start superscript, 6, plus, end superscript cations,
and 7\text{ O}^{2-}7 O2−7, start text, space, O, end text, start superscript,
2, minus, end superscript anions

(Choice D)

1\text{ FeCr}_2^{14+}1 FeCr214+1, start text, space, F, e, C, r, end text,

start subscript, 2, end subscript, start superscript, 14, plus, end
superscript cation and 7\text{ O}^{2-}7 O2−7, start text, space, O, end
text, start superscript, 2, minus, end superscript anions
[Hint 1]

[Hint 2]

\text{Cr}_2\text{O}_7^{2-}start text, C, r, end text, start subscript, 2, end

subscript, start text, O, end text, start subscript, 7, end subscript, start
superscript, 2, minus, end superscript\text{Fe}start text, F, e, end
text(\text{II})left parenthesis, start text, I, I, end text, right
parenthesis\text{Fe}^{2+}start text, F, e, end text, start superscript, 2,
plus, end superscript

\text{Fe}^{2+}start text, F, e, end text, start superscript, 2, plus, end

superscript\text{Cr}_2\text{O}_7^{2-}start text, C, r, end text, start
subscript, 2, end subscript, start text, O, end text, start subscript, 7, end
subscript, start superscript, 2, minus, end superscript
Check
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