(4) An amorphous solid is more probable than a mining the direction of spontaneous reaction, but this

crystalline solid, and a simple crystalline solid more was before the concept of entropy had been clearly
probable than a more complex crystalline solid. recognized. Entropy units are calories per degree
The formation of simpler substances from more per mole, and the entropy changes accompanying
complex ones is therefore favored by the entropy reaction are often only a few entropy units, whereas
change. heats of reaction are commonly more than a kilocalorie
per mole. Thus even though the entropy is multiplied
(5) A molecular addition compound, or a eoordiina- by about 300°K (at ordinary temperatures), the prod-
tion complex, is less probable than its separate com- uct does not even equal one kilocalorie unless the
ponents. entropy is more than 3. If the AH value for a reaction
The formation of such compounds is therefore is relatively large, say -10 kcal per mole or greater,
accompanied by a decrease in entropy, which con- one can reasonably he confident in predicting spon-
sequently increases the requirement of bond strength taneous reaction in that direction.
needed to hold together a stable aggregate.
(6) Compounds of elements of higher atomic weight, Table 5. Comparison of Entholpies ond Free Energies of
or molecules of the free elements themselves, tend to Formotion (kcal mole-') (2)
have higher entropy.
A number of examples are given in Table 3. The
explanation presumably lies in the effects of mass on
the intra-crystalline or intra-molecular vibrations.
The greater the mass, the lower the vibration fre-
quency and thus the more probable the state, and the
higher the entropy. This effect seems to predominate
over minor effects originating in differences among
crystalline forms as shown in Table 4.

Table 3. Effect of Mass on Entropy of Gases at 25'C

(eu) ( 2 ) Table 6. Comparison of Standard Enthalpies and Free
Y = F C1 Rr T
Energies far Some Chemical Reactions
AH AGO

CCldg) + -
2H?O(g) COdg) +
4HCl (g)
(kd)
-41.2
(lkd)
-61.2

--
+
SFak?) 3HdXg) + SOdg) + BHFk) -45.0 -75.9
CaO(e) f COdg) CaCOl(e) -42.5 -31.1
CR'(g)+ 20dg) +
COp(g) 2HzO(g) - 191.8 -191.4

Table 4. Effect of Mass on Entropy of Crystalline Solids

+
AlBrdc)+ PCldg) -
AsClr(1) 3NaF(e) + 3NsCl(e)
+
+
AsFs(g)
A1Cld.z) PBrs(s)
-24.7
-3.1
-31.7
-4.3

(eu) (2)
PbO 16.2
PbS 21.8
TjiaCO1 21 .60
N&Oa 32.5
ZnSO6 29.8
CdSOa 32.8
(7) At ordinary temperatures, entropy effects are
commonly small enough to have relatively little effect
on the direction of reaction unless the difference in
total bonding energy between reactants and products is
relatively small.
This is well illustrated in Table 5 by comparison of
AH and AG values for the formation of a number of
chemical compounds in their standard states, and for a
number of chemical reactions in Table 6. It was
this fact that led Berthelot and Thomsen to believe
that the heat of a reaction was the sole factor deter-
(8) All chemical reactions that increase the entropy
occur spontaneously at high enough temperatures.
Although the heat of reaction changes only relatively
slowly with temperature, the entropy effect is the
product of the entropy and the temperature. No
matter what the heat of reaction, therefore, if the
entropy change is positive and multiplied by a large
enough temperature, the product TAS will be sub-
tracted from the heat of reaction to give a negative
free energy change. This is a very important prin-
ciple, accounting for the existence a t high tempera-
tures of species unknown a t lower temperatures be-
cause of their tendency to form more complex ag-
gregates stable a t the lower temperatures. As already
observed, decompositions of compounds increase the
entropy, and thus tend to proceed spontaneously a t
high enough temperatures.
The special significance of this principle is that
although enthalpy changes tend to dictate the course
of reaction a t ordinary temperatures, the relative
importance of entropy increases at higher temperatures
until it becomes the dominant factor.
Volume 41, Number 1 , January 1964 / 15