-
which would be in aereement with Ortf and Planelles' expression. Unfortunately, my grid has c instead of c2for this ratio even though the expression for Blf on the grid has c2 as do Orti and Planelles. All I can do now is to acknowledge - this inconsistency. To complete the package, four typographical errors might as well be noted. 1. On the e d , in the expression for f l B , the symbol 5 is used instead of the intended q, the electron charge. 2. Also on the grid, the "I" is missing from v2/fi 3. The last sentence of the first paragraph an p 33 has the word "dimensionless"misspelled "dimensionsless". 4. In the denominator of the long numerical expression for f , the unit C (for coulombs)is missing from the magnitude
Displacement, m
of q.
The ultimate outcome of this somewhat less-than-fuKi1ing experience hopefully is a correci sct of relations among these fundamental and important terms. I thank Orti and Planelles for offering theircorrected form of the grid. Literature Cited 1. Steinfeld,3. I. MokcubundRad&ztion, 2nd ed.; ha Re-: Boston, 1985:pp 27 5. 2. Einstein,APhysik. Zeitsch. 1917.XVIIII 121-128.
James E. Sturm Lehigh University Bethlehem. PA 18015
Force vs. displacement for a rubber band (data from Salsideder [1990,67,962]).
sulting equation to calculate interpolated values a t 0.05-m intervals. Piecewise calculation of the area under this curve gives a value of 1.65 J for the reversible work. This value may be compared with the estimate of 1.91J for reversible work calculated with a linear approximation, corresponding to the area under the line drawn between the first and last points on the graph. The area under the step function in the figure represents the work available if the six 100-g masses are removed one a t a time; the total work for this process is 1.33 J . Jonathan Mitschele Saint Joseph's College Windham, ME 04062
Putting Some Snap into Work To the Editor:
The Tested Demonstration "Maximum Work" by John Salzsleder [1990,67,9621 very cleverly illustrates the concept of reversible work. I have several suggestions that I think can add to its instructional value. With rubber bands, the relationship of force and displacement is not, as Salzsleder notes, a linear one. To estimate the reversible work, Salzsleder uses a linear approximation of this relationship. One can use a spring as an alternative to rubber bands; if one takes care to see that the coils do not come into contact at the smallest extension used, the relationship of force and displacement is linear (following Hooke's law), and the calculation of reversible work eives a orecise value. ~ h & are e idvantages to using rubber bands, however. If one stretches a rubber band and quickly touches it to the lips, a slight warming can be felt; if one then unstretches the rubber band and again touches the lips, a slight cooling is apparent. Afew cycles of this process serve to demonstrate auite convincinelv that contraction of a mbher band is an endothermic pro&k This means that the contraction of a rubber band, a spontaneous process, is not driven by a decrease in potential energy, but by a n increase in entropy. This counterintuitive demonstration provides a good introduction to the meaning of the Gibb's free energy function. A further advantage of rubber bands is the nonlinear force-ditlplacemcnt rc?ationship, for it leads to a more genera1 appreciation of the representation of work as the area under.; force versus disolacement curve. One can use the experimental data and n k e r i c a l integration to arrive a t a more orecise result for the reversible work. ~ h & g u r eillustrates one way in which this may be done. In this eraoh. the seven wints dotted are based on data from s&sieder9s article: The &e connecting the data points was generated by fitting a fifth-order polynomial in displacement to the experimental data, then using the re-
Argon-Potassium Atomic Weight Inversion in the Periodic Table To the Editor:
In evolving his periodic classification of elements in the order of increasing atomic weights (A), Medeleeff had to reverse the order a t two places, bringing Co (A = 58.9332) before Ni (A = 58.7100) and Te (A = 127.600)before I (A = 126.9044). Subsequently, when Ar (A = 39.9480) was discovered it had to precede K (A = 39.1020). These constitute three exceptions in the order of atomic weights. When the phenomenon of isotopy was understood, i t was realized that the atomic weight of a naturally occurring element is just the weighted mean of the atomic masses of the isotopes making i t up. However, as the number of stable isotones of an element. as well as their relative abundances varied randomly over wide limits from element to element, atomic weights ceased to be of significance in characterizingelements, and the three exceptions in the periodic table came to be accepted as a fortuitous fact though of no importance. Still it is a curious fact that amongst the hundred odd elements there should be only three exceptions unexplained so far. In the case of the Ar-K inversion, however, an explanation seems to be available in the nuclear characteristics of the naturally occuring isotopes of these elements, which are both triisotopic with following atom percent abundances. 86Ar = 0.34%;38Ar = 0.0640, OAr = 99.6% 3 9 =~93.2240,O ' K = 0.012%;"K = 6.77%
of these nuclides, only 40Kis radioactive decaying by P(88.8%) to 40Ca and by EC (11.2%) to "AK Geochemists Volume 69 Number 8 August 1992
687
hold that the bulk of '"Ar on the earth is ofthe above radiogenic origin. On this assumption, they calculate the age of earth's crust from the ratio of 4oAr/'%. If this oriein of "Ar. which constitutes 99.6% of the total argon, is accepted, the Ar-K inversion in the periodic table is explained. A similar approach is not available in the case of the other two inversions. All naturally occurring cobalt is monoisotipic (''Co) and stable while all the naturally oecuring Ni isotopes are stable. Similarly one finds that all the naturally occurring iodine is monoisotopic (lZ7I)and stable, while the corresponding isobar '27Te is wholly synthetic. ~~~
H. J. Arnikar University of Poona Pune 411 007, India
BUFCALC Crash Corrected
Dear Editor: Afootnote to a paper that I published in the Journal of Chemiml Education ("BUFCALC: A Pmgrarn for the Calculation of Buffers of Specified pH, Ionic Strength, and Buffer Capacity", 1990, 67,150) stated that a copy of the compiled code for BUFCALC could be received from me by sendine a formatted IBM diskette in a ~ostaee-paidselfaddressed envelope. Since publication, I iave &&d dozens of reauests for copies of this Dromam. While the copies I sent o i t were tech&ally corkctIn terms of the b&er calculation, an undetected programming error would intermittently cause the program to crash. This error has been corrected in the most recent version of the program ( 3 1 1 Readers who havelad problems can receive the new version bv sending a diskette as before to my new address below. William J. Lambert
Pfizer Central Research Building 156 Gmton, CT 06340
Imprecise Numben and Incautious Safety Procedure Mar Experiment
To the Editor: I am writing with reference to the articles T h e Cadmium-Sodium Nitrate Reaction" ( I ) and T h e BismuthSodium Nitrate Reaction" (21, by Williani D. Hill, Jr., which appeared in the Journal of Chemical Education in 1990 and 1989, respectively. 1 have two questions regarding these articles, one relating to the use of sigmfkant figures, the other relating to safety.
the products (51.3627 f 0.00019) g implies a relative error in the mass of product of only 4 ppm. I have several questions about this data. The yield is (99.984 r 0.0004)%based on the stated mass of Cd. While there are manv reactions that proceed wantitatively, this level of pre&ion is startlingwhen pkducing transition metal oxides, which are notorious for deviations from stoichiometry. Apparently the author believes that neither CdO nor Biz03 suffer from this problem. My Cotton and Wilkinson, Advanced Inorganic Chemistry states that CdO varies in color with thermal history due to lattice defects so it is possible that at least the CdO composition could vary. I find it somewhat difficult to believe that the original samule masses were adiusted to aeree-within the ranee rep;esented by the prod&t ranges @.0005 gout of 50 g & 10 prim). Even if this level of re~roducibilitywas achieved, pe;
