scientist first.
She taught that “good stuff5 about molal 25 °C (2, 4, 5, 3); this is almost 10 times smaller than the
freezing-point depression and allotropic forms of sulfur and
the combined gas law. I loved it and many of the kids I teach
today love it, too.
My students do complain, but complaints are not rare in
their other classes, either, the teachers tell me. Driver Ed
and Health are “too hard” or too “dull”. History is “not
useful”, and foreign language requires “too much memori-
zing”, etc.
Make no mistake about it, the argument in Krajcik and
Yager’s article is anti-intellectualism. Its roots go back a long
way in professional education. It seeks to draw strength from
popular appeal. Its adherents are kids who want an easier
program, parents who want the appearance of success on
report cards without hassle, a few teachers whose back-
ground is weak or who prefer the authority of newspapers to
textbooks and research articles. It is “democratic” in the
negative, divisive sense of the word.
Teaching objective material does not make a teacher un-
popular or turn off the students. When the graduated high
school students come back from college to see you, they will
thank you for giving them a solid base of understanding and
skills for that tough first year of college chemistry.
Please, give us the “lumber” to build our courses, but let
the “sawdust” filter down into education journals.
S. T. Bond
See https://pubs.acs.org/sharingguidelines for options on how to legitimately share published articles.
Bridgeport High School
Bridgeport, WV 26330
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Solubility Products and Solubility: Plus 9a Change?
To the Editor:
Although Masterman (1) in his article “Ksp Determination
of Calcium Sulfate” has measured the solubility of CaSC>4 in
water, he has not determined the solubility product Ksp. The
relationship (or lack of it) between solubility and Ksp per-
haps needs to be emphasized once again, because it appears
to be something that is discovered and subsequently forgot-
ten with monotonous regularity. In this Journal alone, the
point was fully discussed by Meites et al (2), overlooked by
Sawyer (3), discussed afresh by Martin (4) and neglected by
Masterman (I). Briefly, to equate Ksp to the square of the
solubility of CaS04 is grossly in error, because it ignores (1)
the appreciable ionic strength of the solution (because both
ions are divalent and the salt is not highly insoluble), which
leads to activity coefficients very different from unity, and
(2) the fact that an appreciable proportion of the compound
is present in solution as the undissociated molecule or ion-
pair CaS04(aq), i.e., it is not a strong electrolyte. If these
factors are taken into account then the true thermodynamic
solubility product K$p° aca2+aso42- about 2.5 X 10-5 at
=
Value of Solubility Product of CaS04 in the CRC Handbook.
Edition Ksp
30th (1947) 6.1 X 10-5
39th, 41st, 44th, 49th, 50tha 1.95 X 10"4
53rd, 55-60th, 62nd 2.45 X 10“5
65th, 66th 3.73 X 10"5
67th (1986-1987) 7.1 X 10"5
• No table of solubility products in 46th and 47th editions.
184 Journal of Chemical Education
square of the solubility. Meites et al. (2) make the pertinent
points that (1) the solubility of CaS04 is analogous to that of
a sparingly soluble weak acid such as 2,4,6-triehlorophenol,
(2) it would be better to confine the solubility-product prin-
ciple to univalent salts such as silver bromide or thallous
iodide where there is negligible ion-pairing, and (3) teachers
should seriously consider whether the solubility-product
principle is in fact closely enough related to solubility to
justify its presentation in that context.
The above comments may seem to be rather pedantic, but
their neglect is illustrated in an illuminating way by the
value of the “Solubility Product” for CaS04 quoted in the
CRC Handbook of Chemistry and Physics (7) (hereafter
called the CRC Handbook). I noticed that the value of K&p =
1.9 X 10-4 quoted from it by Masterman (1) was not the same
as that in my own copy. On examining the various editions of
the CRC Handbook available in our laboratories, I obtained
the results shown in the table. Over a period of 40 years the
value given in the CRC Handbook has changed at least four
times (possibly more, I haven’t looked at all editions) with a
range of almost an order of magnitude.
We can now speculate on the reasons for these changes.
There is no information in the CRC Handbook about
sources, except that the three latest editions have used AGf°
values to calculate Ksp (K&p exp (—ArG°/RT) where ArG0/
=
RT AGf°(Ca2+,aq) + AGf°(Sq42-,aq)
=
AGf°(CaS04, c)).
-
The previous value of 2,45 X 10“5 probably comes from ref 5
which was published in 1970; the CRC Handbook value
changed somewhere between the 1969-70 and the 1972-73
editions. The earlier value of 1.95 X 10-4 was almost certain-
ly the square of the solubility, whose value quoted in the
“Physical Constants of Inorganic Compounds” table in the
CRC Handbook has remained constant over the whole peri-
od.
There are several morals to this tale. Always treat tabulat-
ed data in textbooks and compilations with skepticism, espe-
cially if the original source is not given; there is no guarantee
that the compilers have always appreciated the approxima-
tions they have made. Quote the edition as well as the book
from which you obtain data. And do not assume that the
data quoted in the latest edition are necessarily more reli-
able than those from previous editions; in this case the value
of 2.45 X 105 is closest to the “true” thermodynamic value of
ref 5, which was obtained by careful experiments on CaS04
and is, I suspect, more reliable than the values in the most
recent editions that were calculated from general thermody-
namic data obtained from a variety of sources.
Literature Cited
1. Masterman, D. J. Chem. Educ, 1987,64,408-409.
2. Meites, L.; Pode, J. S. F.; Thomas, H. C. J. Chem. Educ. 1966, 43, 667-672.
3. Sawyer, A. K. J. Chem. Educ. 1983,60, 416.
4. Martin, R. B. J. Chem. Educ. 1986,63, 471-472.
5. Gardner, A. W.; Glueckauf, E. Trans. Faraday Soc. 1970, 66,1081-1087.
6. Guenther, W. B. Chemical Equilibrium; Plenum: New York, 1975; pp 172-176.
7. CRC Handbook of Chemistry and Physics; CRC Press: Boca Raton, FL.
John H. Carpenter
Newcastle University
Newcastle upon Tyne, NE1 7RU, UK
Temp.
Editor's Note: A review article "Ion Association, Solubilities, and
10 °c Reduction Potentials in Aqueous Solution” by Russo and Hanania,
10 °C
which begins on page 148 of this issue, also discusses the confusion
25 °C
about CaS04 and places it in the larger context of how aqueous
25 °C
solution concepts should be taught in general chemistry.
25 °C