The Principles of Chemistry, Volume IMendeleyev, Dmitry Ivanovich
Science
The Principles of Chemistry, Volume I
Mendeleyev, Dmitry Ivanovich
Argon; Chemistry; Periodic law
[53] In order to give an idea of the quantity of heat evolved in the
formation of salts I append a table of data for _very dilute
aqueous solutions_ of acids and alkalis, according to the
determinations of Berthelot and Thomsen. The figures are given
in major calories--that is, in thousands of units of heat. For
example, 49 grams of sulphuric acid, H_{2}SO_{4}, taken in a
dilute aqueous solution, when mixed with such an amount of a weak
solution of caustic soda, NaHO, that a neutral salt is formed
(when all the hydrogen of the acid is replaced by the sodium),
evolves 15,800 units of heat.
49 parts of 63 parts of
H_{2}SO_{4} HNO_{3}
NaHO 15·8 13·7
KHO 15·7 13·8
NH_{3} 14·5 12·5
CaO 15·6 13·9
BaO 18·4 13·9
MgO 15·6 13·8
FeO 12·5 10·7 (?)
ZnO 11·7 9·8
Fe_{2}O_{3} 5·7 5·9
These figures cannot be considered as the heat of neutralisation,
because the water here plays an important part. Thus, for
instance, sulphuric acid and caustic soda in dissolving in water
evolve very much heat, and the resultant sodium sulphate very
little; consequently, the amount of heat evolved in an anhydrous
combination will be different from that evolved in a hydrated
combination. Those acids which are not energetic in combining
with the same quantity of alkalis required for the formation of
normal salts of sulphuric or nitric acids always, however, give
less heat. For instance, with caustic soda: carbonic acid gives
10·2, hydrocyanic, 2·9, hydrogen sulphide, 3·9 major calories.
And as feeble bases (for example, Fe_{2}O_{3}) also evolve less
heat than those which are more powerful, so a certain general
correlation between thermochemical data and the degree of
affinity shows itself here, as in other cases (_see_ Chapter II.,
Note 7); this does not, however, give any reason for measuring
the affinity which binds the elements of salts by the heat
of their formation in dilute solutions. This is very clearly
demonstrated by the fact that water is able to decompose many
salts, and is separated in their formation.
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