Академический Документы
Профессиональный Документы
Культура Документы
Lowell M. Schwartz University of Massachusetts, Boston; MA 02125 Not long ago the following'question arose with regard t o a eeneral chemistrv exercise. Students were asked to weieh several pennies on a balance and to calculate the mean we& with oroner regard to sienificant firmres. One student recorded five mensureients: 2.i4, 2.45, 2.%, 2.50, and 2.47 g. In calculating the mean he summed the five weights finding a total of 12.36 g, divided by five on a calculator and obtained 2.4720000 e. In order to write this number with moper sienificant figures, he reasoned correctly as we had taught. figures represent the accuracy or uncertainty of a written number: how to count sienificant firmres in a eiven number: and how t o propagate iignificant ?igure or 2ecimal place counts throueh s i m ~ l e arithmetic o~erations. However. no text that I sa; and "oneof several a r h s p u b l i s h e d inTHls JOUHNAI.~ mentions the limitations of the propagation procedures. Recause this subject appears in virtually all general chemistrv texts. it amears to br of sufficient interest to merit a better Aders&dKg than what currently exists. I have done some numerical exploration towards this end and offer the results in this article. It is hoped that this will stimulate others to do so also. I shall focus on the propagation of significant figures through those arithmetic operations which are of interest in general chemistry: the ubiquitous addition, subtraction, multiplication, division, and also the taking of common logarithms and antilogarithms, which come up in pH, solution equilibria, Nernst equation, and chemical kinetics calculations. Because the word "number" is needed in too many different contexts, I shall adopt the practice of using the word "result" for a number which is calculated from other numbers. These other numbers I will call "data" (or the singular "datum"). Thus "results" are calculated from "data." The rules for addition, subtraction, multiplication, and division are well known and these are set off as rules 1 and 2, respectively, in the opening paragraph. The rules for logarithms and antilogarithms are less well known but are given in several texts. These are: 4 ) When taking common logarithms, if L is the logarithm of A , ( L = log A ) , the number of decimal places in L is the same as the number of significant figures in A . Conversely, if A is the antilogarithm of L , ( A = antilog L or A = l o L ) ,the number of significant figures in A is the same as the number of decimal places in L . The procedures which are numbered 1,2, and 4 above are often called "rules of thumb," a descriptor that implies not only that the procedures are simple t o use but also that they are crude in the sense that they do not always work. The particular ,problems that I wish to explore are ( 1 ) how to propagate significant figures properly under any circumstances and ( 2 ) the specification of those conditions under which the rules of thumb break down. Both these problems require an understanding of the relationship between the uncertainty of a number and the significant figure representation of that number. The specification of how to write a number with significant figures appropriate to its uncertainty has been stated many alternative wavs but mv oreference is: The uncertaintv in the value of a n u m k r shouidbe within the decimal place occupied bv the riehtmost dieit onlv. For examnle. if the uncertaintv in the number 1.006 is f6.05, the uncertainty is within thk hundredths decimal lace and so the number is ~ r o ~ e r l v written 1.00, the rightmost written digit being in ihehuidredtbs place. Or, if the uncertainty in 6398.7 is f25, theuncertainty reaches to the tens place. The units digit 8 and the tenths digit 7 are not significant. Thus the number is properly
. .
1) When numbers are added or subtracted, write the result with the same number of decimal places as the number having the fewest decimal places. 2 ) When numbers are multiplied or divided, write the result with the same number of significant figures as that number having the fewest significant figures. 3 ) Numbers that are exact are treated as if they had infinitely many significant figures. Since all his weighings were to two decimal places, the student followed rule 1 and wrote the sum with two decimal places, as 12.36 g. Then, understanding that the denominator 5 in the division 12.3615 was exact because the count of five weighings was exact, he reasoned that the mean weight was limited by the four significant figures in the sum and so reported his result with four significant figures, as 2.472 g. Meanwhile, we bad explained the meaning of significant figures in terms of those uncertainties which unavoidably creep into most numbers derived from ex~eriment. The more certain or accurate a number, the more significant figures that must be used to convev that level of accuracv. The last sigi nificant digit in a given number has some uncertainty in & value; previous significant digits in that number should be firm. This student saw the inconsistency and asked, "When I weighed each penny, I was sure of the first two digits in the weight, but thethirddigit in the second decimal place was in doubt so the weighings are good to three significant figures. But the average of these weighings seems to be good to four significant figures. How can the average of five numbers each with uncertaintv in the hundredths nlace have uncertaintv in the thousandths place?" Good question. Somewhat he& tantlv and unhaonilv . . . I answered that the rules for combinine significant figures areonly approximateand sometimes lead tu sienificant fieure counts that arr slirhtlv off. I hestitated because I also knew another possible a n s w e r h a t the precision of the mean was meater than that of the individual measurements, and if thestatistical uncertainty of the mean turned out to be less than 0.01 g, the mean should, indeed, be written with three decimal places. However, I later calculated the standard error of the mean as 0.012 g. This confirmed that the statistical uncertainty of the mean as expressed as the standard error estimate was within the hundredths decimal place. Therefore, in this particular case the correct expression for the mean seems to be 2.47, not 2.472 e. This episode demonstrated to me tLt the subject material on significant figures, which I have been teaching for many yeari, has not been entirely correct. T o no a v a i l j searched through general and analytical chemsitry textbooks for some insight into the prohlem. All of the 20 or so books included some discussion of significant figures and all presented virtually the same information: that the number of significant
' F a example. Hurley. F. H.. J. CHEM.OK.. 17, 334 (1940);Pinkerton. R., and Gleit. C. .. J. CHM. OK.. 44,232 (1967); Anderlik. 6.. J. CHEM.EOUC.. 57. 591 (1980l.
Volume 82 Number 8 August 1985
693
to he significant. The analytical concentration of the acid C = 0.072412 M, and a t this low concentration the fraction of the acid which dissociates is substantial. We solve the quadratic equation K. = x2/(C - x), where x is the hydronium ion concentration, and find x = 0.042212 M and the pH is 1.3746. Next, in order to find the proper significant figure count, we must calculate maximum and minimum pH values corresponding to extremes in the uncertainty ranges of the four data: 500 mL, 3.26 g, 90.04 g mol-', and K. = 0.059. The datum 500 mL presents an obstacle. The significant figure count of this number is ambieuous and we cannot oroceed without additional information. Having noted that the particular flask used was marked "Class A" by the manufacturer, we consult a supply-house catalog and find that 500-mL volumetric flasks so marked have a tolerance o f f 0.2 mL. Thus the volume datum is good to four significant figures and should have been written 500.0 mL. The next obstacle is to decide how to combine data uncertainties to actually achieve a maximum in the DH. Usina algebraic or chemical reasonink-, we conclude that <he pH rekdiis maximized by maximizing the volume and the molecular weiaht data and by minimizing the mass and the K , data. (I wili return to this prohlem of reasoning after finishing the calculation.) Thus the maximum pH corresponds to 500.2 mL, 90.05 g mol-',3.25 g, and K. = 0.058, and this turns out to he 1.3779 pH units. Similarly, the minimum pH of 1.3713 is calculated using 4.998 mL, 90.03 g mol-l, 3.27 g, and K . = 0.060. Subtracting the two pH extremes vields an uncertaintv ranee of 0.0063. which mav be the result is &certain inthe expressed as f0.003. ~herefbre, third decimal olace or the fourth sienificant firmre and should be written 1.3?5 pH units. The problem of reasoning how to achieve a maximum or minimum in the result of a complicated calculation is one which some instructors will hesitate to pose to general chemistry students. An alternative procedure exists which circumvents this reasoning prohlem hut which requires more calculational effort and is not quite as rigorous. However, in most circumstances the two procedures yield the same significant figure count for the result. Again, discrepancies may occur in nonlinear cases when data have relativelv . high .. uncertaintiei, i.e.. when several data are each expressed with a sinele - sienificant figure or with no sicnificant tiaures at all (order-of-magnitude&). In the alternative procedure, the uncertainty due to each datum is propagated one a t a time to the result, the absolute values of these propagated uncertainties are summed, and this sum represents the total uncertainty in the result. We illustrate with the same pH prohlem. Corresponding to tht, four h a , we must carry out four more 1'11 (.nlruli~tL~ns in addition to the hase calculation which yirlded pH = l.:l:26 from the original data set:
The total uncertainty due to all four data uncertainties sums to f 0.0033 DH which leads to the same threedecimal-place or four-significant-figure expression of 1.375 pH for the result. Perhaps the verbal descriptions together with the illustrations above suffice to explain the general propagation procedure, hut here is the alternative procedure expressed in symbolic form: Let y he the result of a computation involving one or more, say I, data values xi. Functionally, Each datum xi is uncertain by an amount Axi. Ax; may he known explicitly or may he estimated t o he one unit in the rightmost decimal place of xi. Let Ayj he the uncertainty in y due to Ax;. These are each estimated as the absolute value of the difference between the value y itself and the value of y computed with (xi Ax;) or (xi - Ax;) replacing xi, i.e., for i = 1,2,. . .I,
AY;
(3)
Finally, assuming that y is originally computed to more digits than are significant, y is rounded off as necessary so that Ay reaches to the rightmost decimal place only. Some nrecautions should be observed in imnlementine this procedu;e. First, as we saw with the molecul~r weight datum in the nH orohlem. one sometimes finds that a difference Av; . . .. is apparently exactly zero even though Axi is not zero. This means either that too few digits were retained in the computation of hoth terms subtracted in eqn. (2) or that y is really ~s of an not a function of that articular x;, ~ e r h a because o\,erlooked rancrllation.'~herttmedi-es'are06vious: recompute the difl~rence inem. ( 2 )retaining more digitg,or confirm the cancellation of x; from the function. The second precaution is to he aware of functions in which a particular datum appears more than once and to calculate only a single Ayi f o r t h a t datum. For example, suppose the result is an average molecular weight M of a binary mixture of hypothetical components having molecular weights 40.000 and 44.000 g mol-'. If the mole fraction of the first component is 0.48, one might compute the average molecular weight from The uncertainty in this result is due to three inexact data whose values are 40.000, 44.000, and 0.48. The number 1in eqn. (4) is the sum of hoth mole fractions, and, since this is an exact numher, it propagates no uncertainty to M. Both molecular weiehts are exnrissed with five simificant fieures and " these propagate negligible uncertainty to M when compared to the uncertaintv hv the mole fraction. The un- oro~aeated . . certainty in M is approximately
1) Using an extreme volume of 500.2 mL (499.8 mL would do just as well) and the other three original data, we calculate pH = 1.3747. This differs from the hase pH by 0.0001 and so we conclude that the uncertainty o f f 0.2 mL in the volume propagates to f 0.0001 in the pH. 2) Usine 90.05 e mol-'. 500 0 mL and the other orieinal ' data,we f i n l P = ~ 1.3746 (to four decimal placesjand conclude that the uncertainty in pH due to our estimated f0.01 g mol-' is beyond the fourth decimal place in the DH. We susoect that this uncertainty is nealieihle in comparison t o t h e others in this prohiem. ~ h u we s choose not to repeat the calculations carrying more digits in an effort to find an explicit uncertainty in the pH due to the molecular weight uncertainty. 3) With a mass of 3.27 g and the other original data, we calculate pH = 1.3736, which, when compared to the hase, yields an uncertainty o f f 0.0010 pH units. 4) Using K. = 0.060 and the other original data, we find pH = 1.3724 and n propagated unrertainty o f f 0.0022 pH.
and observing that this uncertainty reaches to the hundredths place in M, the proper representation is 42.08, with four significant figures. However, if one mistakenly treats hoth numbers 0.48 in eqn. (4) as independent data, these would propagate f0.40 and f0.44 uncertainties to M, which are clearly erroneous. This example shows that the procedure may not always be applied blindly to a numerical computation without some knowledge of the meanings associated with the data values. Parenthetically, the rules of thumb break down drastically in this example. By these rules hoth terms of the sum in eqn. (4) are good to two significant figures because both terms are multiplications limited by the two significant f w e s Volume 62 Number 8 August 1985
695
of the mole fractions. The sum of these two terms. hoth mod to the units place, yields a value of M also with$ignifi>ant dieits onlv to the units nlace. Thus the rules of thumb dictate t h i t M ii42, good to t a o significant figures rather than the correct four significant figures. This general procedure is useful for propagating significant fieures from data to a c o m ~ u t e d result in cases where no rule i l l suffice. Given that ofthumb exists a t all. A s&gle example w the N-H bond distance and the bond angles in ammonia are 0.1008 nm and 107.3", respectively, calcdate the H-H bond distance. My geometrical construction leads to the calculation (O.l008)(2)sin (107.3/2) = 0.16237 nm for the H-H distance. With no further information available, I propagate f 0.0001 nm and f O . 1 in N-H length and angle, respectively. A recalculation using 0.1009 nm and 10'7.4' yields a maximum H-H distance of 0.16264 nm. Thus the uncertainty in the result is in the fourth decimal place and the appropriate significant fieure exnression is 0.1624 nm. A well-!&own alternative procedure exists for the special case when the result is computed by multiplication and/or division of data. I t can he easily shown2 that the relative uncertaintv of the result eauals the sum of the relative uncertainties of the data in these circumstances. Hence, the uncertainty in the result y is This is entirely equivalent to eqn. (3), and which procedure to use for multiplicationldivision is largely a matter of personal preference. Success or Failure of Rules of Thumb The final problem to be addressed is to seek to define those circumstances under which the rules of thumb break down. This is a simple matter for additionlsuhtraction. If the uncertainty in each datum is assumed to he f1 unit in the riRhrmoit decimal place, then this rule hrraks down when a result involves ten or more additions andlor subtractions of data all having the same limiting numher of decimal places. The total uncertainty propagated to the result from these data reaches to the next higher decimal place. Thus the rightmost significant digit is a t that higher decimal place. Unfortunately, it does not seem nossible to summarize the break down circumstances for &ultiplication/division as simply as for additionlsuhtraction. I have done emnirical calculations to test ftn success or failure oi these rules and will shuw these results in tabular form. Perhaw interested readers will accent the challenge of finding more concise ways of expressing these results. Empirical testingfor the success or failure of the multiplication rule of thumh involves computing significant figures for the result y = xn, where x is a datum with a specified numher of significant figures. The testing procedure is the same as that used in the examples of success versus failure given above. For example, consider the case y = 2.003 where y = 8.00 has three significant figures according to the rule of thumb. The uncertainty in this y is f 1Z.013 - 8.001 = f0.12 which reaches to the tenths decimal place. Therefore, only two digits in y are significant and the rule fails. By contrast, however, in the case y = 2.004, y = 16.0 has three significant figures hy the rule of thumh and its uncertainty is f0.32. Thus the tenths digit is again significant but the result carries three significant figures and so the rule of thumh succeeds. The table shows some of the results of these tests. the upper table for data carrying one significant figure and the lower table for two simificant fieures. Each row shows the in the first column and each column tests for the datum
shows the tests for the nower n eiven in the ton row. The entries in the body of thk table g e integers or 'marks. An integer represents the numher of significant figures in the corresponding result y as computed by the test and an X indicates that the uncertainty in y is so large that y cannot be written properly even with a single significant figure. Thus the rule of thumb for multinlication is successful for a eiven x n only if the corresponding tabular entry matches the numher of significant figures taken for x. In the upper table
Success or Fallure of the Rule of Thumb tor Multlplicatlon as Amlied to the ComDutation x"
1 Significant Figure
x
1 2 3 4 5 6 7 8 9
2 . 1 . 1 . 1 . 2 . 1 . 1 . 1 . 1 . 1
3 l X 1 1 2 1 1 1 1
4 X 1 X 1 1 1 1 1 1
5 X X l 1 1 1 1 1 1
6 X X X X 1 1 l 1 1
7 6 9 10 11 12 13 X X X X X X X X X X X X X X X X X X X X X l X X 1 X X X X X 1 X X X X 1 1 1 X X X l X X l 1 1 1 X 1 1 1 1 X X X 1 1 1 1 1 1 1
14 X X X X X X X X 1
15 X X X X X X X X 1
16 X X X X X X X X 1
17 X X X X X X X X 1
16 X X X X X X X X 1
19 X X X X X X X X 1
20 X X X X X X X X 1
"=
2 Significant Figures 15 16 17 18 19 20 1 1 1 1 1 1 1 1 1 1 2 1 1 1 1 2 2 1 1 2 1 1 1 1 1 1 1 1 1 1 1 2 1 1 2 1 1 2 1 1 1 1 1 1 1 1 1 1 1 1 2 1 2 1 1 2 1 1 2 1 1 1 X 1 1 1 1 1 1 2 1 2 1 2 1 1 2 1 1 2 1 x X x x 1 1 1 1 1 1 1 2 1 2 1 1 2 1 1 1 x X 1 1 1 X X 1 1 1 1 1 2 1 2 1 1 2 1
See fcn example: Swartz. C. E.. "Used Maih for the First Two Years o f College Science, Prentice-Hall, Inc.. Englewood Cliffs, NJ, 1973, p.
9.
696
onlv 1's indicate successful a ~ d i c a t i o n of s the rule, and only 37% of these applications ar~mccessful. In the lower table, onlv 2's indicate success and here the success rate is about 60%. ~uicess rates for similar testing using x values with more significant figures (not shown) do not exceed 63.3%. We observe that the test results are somewhat erratic and thus difficult to express concisely. The rule of thumb is most successful for data which round to a 9 but fails even for simple squares if x rounds to a 4. Similar patterns of successes and failures occur for higher significant figure data. I have also examined the success/failure pattern for the loearithm and antiloearithm rules of thumb and in these cases t h Y e results can be suknarized easily. For common logarithms the rule yields the correct number of decimal places in the result or i t yields one decimal place too few depending on the value and on the significant figure count of the datum. Suppose the result y i;log x, where the datum x may be in any order bf magnitude hut is written with k significant figures. 0 " . ' It is convenikt to express x in the exponential form z 2 1 where 0.1 5 z < 1.The number of significant figures in z is k regardless of m. When k is large and when f1unit uncertainty is assumed in the k t h significant digit, the transition from successful to unsuccessful application of the logarithm rule of thumb occurs a t z = loge = 0.43429. . . This statement is justified by an argumentgiven in the Appendix. If k is not large, the transition occurs at z values slightly below loge; these transitions are summarized as follows: Significant figures in x 1 1 2 2 3 3 Correct decimal places in log x l i f z 50.3 2ifz 20.4 2 if z < 0.42 3 if z 2 0.43 3 if z 5 0.433 4 if z 2 0.434
large k large k
> 0.63778. .
for propagating significant figures through arithmetic calculations frequently yield misleading results. Two procedures are available for performing this propagation more generally and more reliahlv than the rules of thumb, hut both procedures require considerably more calculational effort than do the rules. I n seeking an understanding of those conditions under which the rules succeed or fail I have examined the operations of addition/subtraction, multiplication, common logarithms and antilogarithms. T h e operation of division remains to be studied as well as the many calculations eucountered in chemistry which involve two or more rules. The calculation of the arithmetic mean discussed in the opening paragraph is such as example. I hope this paper will stimulate others to offer contributions toward these unsolved problems.
Appendlx
Consider the propagation of significant figures from the datum x form zlOm,where 0.1 5 z < 1. The uncertainty in 1: is Ax and the leftmost non-zero digit in Ax reaches to the kth significant figure of x . The uncertainty in y which is Ay = llog(x +Ax) -log x i = log(1 + Axlx). Ask increases, Adz decreases and Ay approaches the first term of the Taylor series expansion which is (log e)Ar/x. The ratio Axlz is the same as the relative uncertainty Adz. Because the leftmost non-zerodigit in Az is in the place of the kth significant figure of 2 , we can write & asp X lo-' andp will be 1or more but less than 10. The ratio Adz or Axlx becomes p x 10-klr so tht Ay becomes p(log e)/z X The leftmostnon-zerodigit in the coefficientp(log e)lz determines the orooer siznificantfizure reoresentation of v. If this leftmost non-ze;o dieit isuiin the units olaci. . . "v will be eood'to k derimnl places and that will he the case u hrn p = I rrorrespondind t o + I unit uncertainty in rhr kthsiynilicanr figurrolxland whrnz is less than loge. Thus the rule of thumb is correct under these circumstances. But far p = 1and values of z greater than log e , the uncertainty in y reaches only to the (k + 1)thdecimal place and the rule of thumb has underestimated the correct number of decimal olaces ofy by one. Now consider y = 10' where the datum x has integer part rn and decimal fraction 2 which is good to k decimal places. The uncertainty Az in z is assumed to be p X 10Wkand this propagates an uncertainty toy whichis Ay = llOr+A* - 10"l = lO"lexp(hrlloge) - ll.Ifk is large, A 2 is small, exp(&llog e) approaches (1 + Ar(log el-'), and Ay approaches Az(loge)-'(10") whichcan he writtenp(lO*llog elThe 10-klOm.This latter quantity is to hecompared with y = 10210m. coefficient 10' in y has avalue in the range 15 10' < 10 because 0 5 2 < 1. The corresponding coefficient in Ay is p(l0'llog e)lO-k. If p(lOZllage) is ten or above, the uncertainty Ay will reach to the (k - 1)th decimal place and, therefore, y itself will be uncertain in its kth significant figure, a success for the rule of thumb. However, if p(lOZlloge)< 10, the uncertainty will reach only to the kth decimal place which is the (k + 1)th significant figure ofy. The rule of thumb in this ease has underestimated the proper significant figure count hv one. Thus the transition between success and failure of the rule o E thumh for antiloearithms is at that r value for which o lO'/loe e ~"~ = 1Uond rhat rrirloll2 is I + loglloge~ - lugp. Ifp = I,wrrrapunding to 11 unit uncertainty in the klhdrcirl~al placauiz, tlwoitical~i.; at 1+ log(1oge) which is 0.63718. . .
to the result y = logl@.The datum is transformed if necessary to the
large k large k
The meaning of this table can be illustrated by again examining the pK.'s corresponding t o K. of 2.35 X 10-3 and 9.35 X 10-3 both of which have k = 3 significant figures. Withz = 0.235, which is less than 0.43, we see that the corresponding pK,is written 1.629, with three decimal places. But with z = 0.935, which is neater than 0.433, the correct expression is pK. = 1.0292. with-four decimal places. For anttlogirrithms, the rule of thumh arain is either correct or off by onLsignificant figure dependinion the value of the datum and its decimal place count. Suppose y = loz, where x is a datum having integer part m and decimal fraction z which is good to k decimal places. Again according to an analysis given in the Appendix, we see that for large k and for f 1unit uncertainty in that k t h place, the transition between success and failure of the rule of thumb is a t the z value of (1 + log(log e)) = 0.63778. . . For z values above this transition the rule of thumb is correct and below the transition, the rule yields one significant figure too few. If k is small, the transitional z is somewhat less than this value as is shown a t the top of the next column. Thus if pK, = 4.52 with z = 0.52 and k = 2 decimal places, the corresponding K. = 3.02 X 10-5, with three significant figures. But if pK. = 4.72 withz = 0.72, the corresponding pK, is 1.9 X lOW, with two significant figures.
Summary
~~
~~
~.
Volume 62
Number 8
August 1985
897