It is very important to recognize that an ion is very different from the corresponding

neutral atom. A metal ion is formed form the atom by the loss of n electrons, where n is
equal to the valency of the metal (e.g., K – e– → K+, univalent metal; Ca – 2 e– → Ca2+,
divalent metal). Similarly, a nonmetallic ion is formed from the corresponding atom by the
gain of electrons equal in number to the valency of the nonmetal (e.g., 0.5 Cl2 + e– → Cl–,
univalent nonmetal; S + 2 e– → S2–, divalent nonmetal). Their electrical charges impart to
the ions properties quite different from those of the corresponding (electrically neutral)
atoms. Ions do not behave in the same way as atoms. For example, by dissolving electrically
neutral, molecular chlorine in water, a solution is produced which is yellow in color and is
a vigorous bleaching agent; however, a solution containing chloride ions (Cl–) has neither
of these properties. Similarly, a sodium atom will act immediately upon water, whereas a
sodium ion (Na+) can exist in water without acting upon water in any way. Since most salts
are ionized in solution, the reactions involving them occur between ions. For example,
when sodium chloride is added to silver nitrate solution, the free silver ions and the free
chloride ions react and form insoluble silver chloride, which is precipitated. The free sodium ions and the free nitrate
ions do not take part in the reaction. Instead of the chemical
equation:
AgNO3 + NaCl = AgCl + NaNO3,
a better representative expression is:
Ag+ + NO3– + Na+ + Cl– = AgCl + Na+ + NO3–
or, since the sodium and nitrate ions are not involved, the ionic equation: Ag+ + Cl– = AgCl.
In an ionic equation, the sum of the positive and the negative charges must be the same on
both sides:
(2 NO2– + 2 I– + 4 H+ = I2 + 2 NO + 2 H2O; 2 Fe(CN)64– + Cl2 = 2 Fe(CN)63– + 2 Cl–)
In the case of ions, it is seen that oxidation is associated with an increase in the positive
charge of a cation, e.g., Fe2+ becomes Fe3+, and reduction involves a decrease in the positive
cation charge. In the case of anions, a decrease in the negative charge corresponds to oxidation, and an increase in
the negative charge to reduction: the ferrocyanide ion, Fe(CN)64–, is
oxidized to the ferricyanide ion, Fe(CN)63–, and the manganate ion, MnO42–, is oxidized to
the permanganate ion MnO4–. Changes in the principal valency of the metal atom in the ion
take place here: bivalent iron in Fe(CN)64– becomes trivalent in Fe(CN)63–, and hexavalent
manganese in MnO42– becomes heptavalent manganese in MnO4–. If the main valency of
the metals is treated as positive, and that of oxygen, the halogens, and negative radicals as
negative, the ionic charges may be found. Since the net charge must remain constant in an
ionic reaction, oxidation and reduction must take place simultaneously, with some members undergoing oxidation
and others reduction.
The tests for metallic and acid radicals in chemical analysis are essentially tests for ions.
For example, all soluble silver salts release silver ions in solution in water; likewise, all
584 6 Electrometallurgy
State Example Type of conductivity
Solid
Metals Electronic conductor
Nonmetalic graphite Electronic conductor
Compounds:
Manganese oxide
Sulfides (copper, molybdenum, lead)
Electronic conductor
Electronic conductor
Carbides Electronic conductor
Oxides:
Doped zirconia, yttria and thoria
Other oxides (magnesia, alumina, etc.)
Electrolytic conductor
Nonconductors
Liquid
Water Electrolytic conductor*
Aqueous solutions Electrolytic conductor
Mercury Electronic conductor
Organic acids Weak electrolytic conductor
Molten salts Electrolytic conductor
 Organic compounds (alcohols, carbon tetrachloride, etc.) Nonconductor
soluble chloride salts release chloride ions in solution. When a solution of a silver salt is
treated with a solution of a chloride salt, the positively charged silver ions and the negatively charged chloride ions
are mutually attracted, combine, and form a precipitate of
insoluble silver chloride (AgCl). The precipitate dissolves in NH4(OH) and is insoluble in
HNO
3. It is, therefore, possible to identify any soluble silver salt by using dilute HCl, and
any soluble chloride by using a solution of AgNO3