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The process of discovery: Mendeleev and the periodic law


Don C. Rawson
a a

Iowa State University, Ames, Iowa, 50010, U.S.A. Version of record first published: 22 Aug 2006.

To cite this article: Don C. Rawson (1974): The process of discovery: Mendeleev and the periodic law, Annals of Science, 31:3, 181-204 To link to this article: http://dx.doi.org/10.1080/00033797400200221

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ANNALS OF SCIENCE
A N I N T E R N A T I O N A L REVIEW OF THE HISTORY OF SCIENCE A N D TECHNOLOGY SINCE THE RENAISSANCE

Vol. 31
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May, 1974

No. 3

T H E PROCESS OF DISCOVEI~u M E N D E L E E V AND T H E P E R I O D I C LAW B y DoN C. RAwsoN*


CONTENTS 1. 2. 3. 4. 5. 6. 7. INTRODUCTION PRESENTIMENTS AND FALLACIES: MENDELEEV'S PI~-CURSORS ALGEBRAIC PROGRESSIONS AND ' PRIMARY MATTER ' EVALUATION OF MENDELEEV'S PRECURSORS MENDELEEV'S INTEREST IN THE PROBLEM RECOGNITION OF THE LAW CONFIRMATION PAGE 181 183 187 190 190 194 203

1. Introduction
IN the century that has passed since D. I. Mendeleev announced his discovery of the Periodic Law of the Elements in 1869, chemists and historians of science alike have acknowledged his work in chemical classification as a fundamental contribution to our store of scientific knowledge. However, those who have written about the method of his discovery have usually only briefly and incompletely explained it, without adequately relating his work to that of other chemists who preceded him and without tracing explicitly the steps by which Mendeleev arrived at his conclusions. The publication within the past few years of many archival materials dealing with Mendeleev's work has provided new information, which is extremely useful in explaining the method of his discovery, both in regard to the extent to which he relied on the accomplishments of his precursors and the penetrating inquiry of his own. A general method of scientific discovery is not easily defined. On occasion, sudden intuition may enable a scientist to discern relationships in data over which he has laboriously puzzled. Usually, however, the discovery of something so fundamental as a natural law is an accumulative process. In Mendeleev's case the evidence indicates that his discovery of the Periodic Law followed the course that he himself later described as the usual process in the discovery of any natural law: (1) presentiments that the law exists; (2) recognition of the significance of
* A s s i s t a n t Professor of H i s t o r y , I o w a S t a t e U n i v e r s i t y , A m e s , I o w a 50010, U.S.A. A.S. N

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the law; and (3) confirmation of the law by experimentation. 1 If one accepts the validity of this sequence, he may also agree that although all three steps are essential, the second - - t h e recognition of the significance of the law--is probably the most crucial, for this is the ' breakt h r o u g h ' from simply accumulating and arranging particular data to deriving generalizations. For the half-century prior to Mendeleev's work, various chemists held the presentiment that the elements were related mathematically, probably according to their properties and atomic weights. Mendeleev acknowledged that at the time he began working on a system of the elements he was familiar with the work of several of these chemists, namely, Gladstone, Kremers, Lenssen, Dumas, and Pettcnkofer; and he remarked that their investigations encouraged him to seek the law governing the relationship of the elements. ~ The question then arises: why was it Mendeleev and not they who recognized and explicated the law underlying these chemical relationships? The reasons are no doubt manifold, but two stand foremost. First, as Mendeleev's precursors theorized on the problem of systematizing the elements, they often became overly intrigued by apparent, but misleading, numerical relationships, which impeded their search for the actual unif$ing principle. In particular, they were drawn to the notion that the atomic weights of analogous elements increased by regular increments, often forming ' t r i a d s ' of elements. In some instances they also believed that their numerical relationships provided evidence that a ' primary matter ' served as the basic structural unit for increasingly complex elements. Although Mendeleev profited from the presentiments that the elements were related according to their atomic weights, he did not become bound to faulty assumptions involving ingenious numerical relationships. Second, by the late 1860s, Mendeleev had at his disposal more accurate values for many atomic weights than were available even a decade earlier and, more important, a clearer definition of atomic weights, which had been commonly confused with equivalent weights. Thus free from several basic misconceptions and utilizing sounder data, he proceeded from those presentiments he shared with his precursors to a step-by-step comparison not only of analogous elements within groups (such as the alkali metals), as his precursors had done; but also of dissimilar elements, an inquiry the others had only touched upon. Through this creative process Mendeleev finally related all of the elements in a system, in which
1 D. I. Mendeleev, Periodicheskii zakon: Osnovnye stat'i, Moscow, 1958, pp. 314-315, reprinted from Chapter 15 of Oenovy khimii, 8th edition. Zhurnal russkago fiziko-khimicheskago obshchestva, 1869, I t 60-77; Mendeleev, Perio. dicheskii zakon, p. 314.

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their properties are a periodic function of their atomic weights. This was the point of recognition, and NIendeleev promptly announced the principle of periodicity as a genuine law of nature. 3 Confirmation of the law came later through the experimentation of other chemists.
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2. Presentiments and Fallacies: Mendeleev' s Precursors The intrigue of numbers, which captivated Mendeleev's precursors, appeared in several persistent concepts but probably most strikingly in the compelling notion of the ' triads '. First postulated b y Johann Wolfgang DSbereiner, a pioneer in stoichiometric studies at the University of Jena, in 1817, it awaited elaboration a generation later b y J. H. Gladstone, Peter Kremers, and Ernst Lenssen. In essence it stated that ibr various three-member groups of analogous elements, the atomic (or equivalent) weight of the middle member is the mean of the other two. Initially, DSbereiner suggested this relationship for calcium-strontiumbarium (27.5-50-72.6); 4 then, in 1829, having accumulated more data, he added chlorine-bromine-iodine (35-47-78.38-126.47), lithium-sodiumpotassium (15.25-46.54-78.39), and sulphur-selenium-tellurium (32.2479.26-129.24). Although the weights of the middle members only approximated the theoretical means, D5bereiner was so struck by these relationships that he concluded they reflected a general principle of nature-a principle, which, however, he could not yet identify. 5 Nor could others who later pursued the notion of the triads provide a principle to explain the seemingly significant numerical relationships they detected. This was true of John Hall Gladstone, lecturer in chemistry
a I t s h o u l d be a c k a o w l e d g e d t h a t a t a p p r o x i m a t e l y t h e t i m e o f M e n d e l e e v ' s d i s c o v e r y s e v e r a l o t h e r c h e m i s t s - - A . E. B ~ g u y e r de Chaneourtois, J. A. 1%. N e w l a n d s , W i l l i a m Odling, G u s t a v u s I-Iinrichs, a n d L o t h a r M e y e r - - w e r e w o r k i n g i n d e p e n d e n t l y on s y s t e m s of classification i n v o l v i n g periodicity. A l t h o u g h t h e s e m e n e x h i b i t e d considerable originality a n d insight, n o n e of t h e m s e e m s to h a v e recognized t h e significance of t h e principle t o w a r d w h i c h his i n v e s t i g a t i o n w a s leading as c o m p l e t e l y as d i d Mendeleev. I n a n y case, it is n o t m y p u r p o s e to a r g u e t h e q u e s t i o n of precedence in t h e d i s c o v e r y of t h e Periodic L a w n o r to d i m i n i s h t h e i m p o r t a n c e of M e n d e l e e v ' s c o n t e m p o r a r i e s , b u t to explain t h e process o f M e n d e l e e v ' s o w n investigation. Since M e n d e l e e v w a s u n a c q u a i n t e d w i t h t h e w o r k of t h e s e m e n a t t h e t i m e of his discovery, I h a v e l i m i t e d t h e p r e s e n t s t u d y to c h e m i s t s who c o n t r i b u t e d to t h e p a r t i c u l a r c o n t e x t in w h i c h M e n d e l e e v p u r s u e d his inquiry, t h a t is, G l a d s t o n e , K r e m e r s , L e n s s e n , D u m a s , a n d P e t t e n k o f e r . F o r t h e m o s t r e c e n t s t u d i e s on t h e general q u e s t i o n of c o n t r i b u t o r s to c h e m i c a l classification a n d t h e p a r t i c u l a r q u e s t i o n of precedence, see J. W. v a n Spronson, The Periodic Syste~r* of Chemical Elements: A History of the First Hundred Years, A m s t e r d a m , 1969; a n d H e i n z C a s s e b a u m a n d George B. K a u f f m a n , ' T h e Periodic S y s t e m of Chemical E l e m e n t s : T h e Search for I t s Discoverer ', Isis, 1971, 62, 314-327. 4 Ann. der Phys. (Gilbert), 1817, 56, 331-334. 5Ann. der Phys. und Chemic (Poggendorff), 1829, 15, 301-307. D 6 b e r e i n e r ' s occasional d o u b l i n g of e q u i v a l e n t weights, e.g. l i t h i u m - s o d i u m - p o t a s s i u m , reflects t h e u n c e r t a i n t y over chemical c o m b i n a t i o n still e x t a n t a m o n g c h e m i s t s a t this time.

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D o n C. R a w s o n

a t St. T h o m a s H o s p i t a l in L o n d o n a n d Fellow of the R o y a l Society, who r e p e a t e d D 6 b e r e i n e r ' s grouping in 1853, a l t h o u g h with m o r e accur a t e l y d e t e r m i n e d weights a n d a firmer defirdtion of equivalency: 6

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Li = 6-5 N a = 23 K = 39.2 C1 = 35.5 B r = 80 I =127.1

Ca = 2 0 Sr = 4 3 . 8 Ba =68.5 S =16 Se = 3 9 . 5 Te --64.2

The s a m e deficiency a p p e a r e d w h e n P e t e r K r e m e r s of K61n published an e x t e n d e d t a b l e of triads in 1856: ~ Li = 6.5 N a = 23 K --39"2 C a - - 20 Sr = 43.8 B a -- 68.5 H g ~- 100 P b = 103.7 Ag --108.1 C1 = 3 5 . 5 Br -- 80 I = 127.1 S = 16 Cr = 2 6 . 7 Se ~-39.5 S =16 Se = 3 9 . 5 Te = 6 4 . 2 Cr = 2 6 . 7 Mo = 46 V =68"6 P =31 As = 75 Sb -- 120.3

H o w e v e r , K r e m e r s did a d d a significant c o m p o n e n t to the whole question of relationships, when he suggested a bi-directional scheme of ' c o n j u g a t e d t r i a d s ', in which c e r t a i n e l e m e n t s serve as m e m b e r s of two triads. For example: Li = 6.5 Na =23 K = 39.2 Mg = 12 Zn = 32.6 Cd = 56 Ca = 2 0 Sr = 4 3 . 8 Ba =68.5 B o t h horizontially a n d vertically, K r e m e r s o b s e r v e d , t h e weight of the middle m e m b e r is a p p r o x i m a t e l y t h e m e a n of the o t h e r two. s Although K r e m e r s a p p a r e n t l y did n o t a p p r e c i a t e the i m p o r t a n c e of this step, he h a d b r o k e n new g r o u n d b y c o m p a r i n g n o t o n l y analogous e l e m e n t s within i n d e p e n d e n t groups, b u t also groups of dissimilar elements. This bi-directional m o d e of c o m p a r i s o n l a t e r p r o v e d to be one of the k e y s to ~ e n d e l e e v ' s recognition of t h e Periodic Law.
Phil. Mag. and Jour. Sci., 1853, (Ser 4), 5, 314-320. Ann. der Phys. und Chem. (Poggendor~), 1856, 99, 58-63. 8 Ibid., 1857, 100, 261-270.

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Mendeleev also profited f r o m the investigation of t h e t r i a d s b y a n o t h e r chemist who joilled t h e search for n u m e r i c a l r e l a t i o n s h i p s - - E r n s t Lenssen, a y o u n g a s s i s t a n t to Professor K a r l Reining/us Fresenius a t Wiesbaden. L e n s s e n e x t e n d e d the notion of t h e t r i a d s to include all of the known e l e m e n t s b y dividing t h e m into t w e n t y triads, according to their metallic or n o n - m e t a l l i c properties, placing h y d r o g e n s e p a r a t e l y a n d m e r c u r y in each of t w o triads, one metallic a n d one n o n - m e t a l l i c 2

r
1. Li Na K 6.95 23.0 39.11 (ai + K)/2 = 23-03 Ca Sr Ba 20 43.67 68.59 (Ca + Ba)/2 = 44.29 Mg ZnCd 12 32.5 55.7 (Mg + Cd)/2 = 33.8 Mn FeCo 27.5 28 29.5 (Mn + Co)/2 = 28.5 La Ce Di 47 47.3 49.6 (La + Di)/2 = 48.3 Y-----Eb 32.2 ? Tb ?

H 1
11.

,
C N 6 7 (C + 0 ) / 2 = 7 O 8

2.

12.

F B Si 9"5 11 15 (F + Si)/2 = 12"2 C1 Br I 17.7 40 63.5 (C1 + I)/2 = 40.6 S -Se Te 16 39.7 64-2 (S + T e ) / 2 - - 40.1 P As Sb 16 37.5 60 (P + Sb)/2 = 38 Ti Sn Ta 25 59 92.3 (Ti + Ta)/2 = 58.7 Mo V W 46 68.5 92 (Mo + W)/2 = 69 Rh Ru Pd 51.2 52"1 53"2 ( R h + P d ) / 2 = 52.2 Ir----Pt Os 98.5 99 99.4 (Ir + Os)/2 = 98.9 Au Hg Bi 98.4 100 104 (Au + Bi)/2 = 101.2

3.

13.

4.

14.

5.

15.

6.

16.

7.

A1 -No= Th 13.7 ? 59.5 (A1 + Th)/2 = 36.6 Be Zr U 7 33.6 60 (Be + U)/2 = 33.5 Cr Ni Cu 26.8 29.6 31.7 (Cr + Cu)/2 = 29.3 Hg Pb Ag 100 103.6 108 (Hg + Ag)/2 = 104

17.

8.

18.

9.

19.

10.

20.

9 A n n . der Chem. u n d P h a r m . ,

1857, 103, 121-131.

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I n addition1 Lenssen combined these triads into groups of three triads each (hydrogen serving as a ' t r i a d '), the m e a n equivalent weights of each middle triad lying a p p r o x i m a t e l y halfway between the m e a n weights of the o t h e r two triads in the group.

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Triad
1

Mean equivalent weight 23 33 44 28 ? 47 29.5 33.5 37 1 7 12 38 40 40 52.1 61 69 99 101 104 (29.5 + 37)/2 = 33.3 (23 + 44)/2 = 33.5

3 2 4 6 5 9 8 7 H 11 12 15 14 13 18 16 17 19 20 10

(1 + 12)/2 = 6.5

(38 + 40)/2 = 39

(52.1 + 69)/2 = 60.6

(99 + 104)/2 = 101.5

Several of the triads in Lenssen's scheme were those previously used b y DSbereiner, Gladstone, and Kremcrs; the others Lenssen added himself. In some cases t h e y did not fit t o g e t h e r adequately, either according to their equivalent weights or t h e i r chemical properties. F o r example, Lenssen placed fluorine with boron and silicon (Group 12), where in atomic weight it corresponded o n l y roughly and in properties a o t a t all. E v i d e n t l y Lenssen realized t h a t some of his triads did not display v e r y precise m a t h e m a t i c a l relationships, and he suggested t h a t these might actually be ' diads ', each with an ' a t t a c h e d ' member. This, however, provided no real explanation for the discrepancies, either in equivalent weights or in properties. Moreover, Lenssen's system left no room for undiscovered elements. W h a t Lenssen did contribute was an

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a t t e m p t to include all of the k n o w n elements in a single system; w h a t he lacked for his system, as 1Vfendeleev later pointed out, was an underlying principle.

3.

Algebraic Progressions and ' Primary Matter '

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I n 1857, J e a n - B a p t i s t e D m n a s , the p r o m i n e n t ~'rench chemist, who for years d o m i n a t e d scientific life a t the Sorbonne, a d d e d a new theoretical c o m p o n e n t to the search for a s y s t e m o f the elements, although it led no closer to a principle. I n a l e n g t h y exposition, D u m a s rejected the notion of triads, even to the limited e x t e n t t h a t Gladstone h a d e m p l o y e d it, devising instead a complex algebraic set of increments, which he insisted could a c c o u n t for the relationship of the elements. P r o m p t e d b y the homologous series a p p a r e n t in organic c o m p o u n d s , whose members could be related algebraically, D u m a s proposed the following scheme: x0 F C1 Br I N P As Sb Bi C B Si Zr 0 S Se Te Mg Ca Sr Ba Pb = 19 = 19 = 35-5=19+16-5 = 80 = 1 9 + 3 3 428 =127 =19+33 +56419 = 14 = 31 = 75 =119 =207 = 6 = ll = 21 = 66 = 8 = 16 = 40 = 64 = 12 = 20 = 44 = 68 =104 = 14 =14+17 =14+17444 =14+17+88 =14+174176 =6 =64 5 =6415 =6+60 =8 =8+ 8 =8+32 =8+56 = 12 =12+ 8 =12+32 = 12456 =24+80 a a4 a+ a+ a a+ a4 a4 a4 d 2d+d' 2d42d'+d" d d 4 d' d+2d' d+4d'

a a+ d a 4 3d adl2d a a+ a+ a4 d 4d 7d

a a+ d a + 4d a + 7d 2 a + 1 0 d 11

lo Comptes Rendus, 1857, 45, 709-731, e x p a n d e d a n d s o m e w h a t modified b y D u m a s in A n n . de chem. et de phys., 1859, 105, 129-210. 11 I n order to h a v e avoided the anomalous 2a for lead, D u m a s would need to huve calculated lead as 12+ 8 0 + 12, or a + 10d+ d' ; b u t d' first a p p e a r i n g for the .fifth element of the g r o u p 8nd equal to a would have been as anomalous as the 2a. E v i d e n t l y lead did not fit properly into D u m a s ' s algebraic scheme.

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Dumas also showed certain numerical relationships between dissimilar elements, a comparison thus far touched on only by Kremers: Increment

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N P As Sb
o

= 14 = 31 = 75 =122
= 8

F C1 Br I
Mg

~ = = =
=

19 35"5 80 127
12

5 5 5 5
4

S Se Te Os

=16 =39.75 =64.5 =99"5

Ca Sr Ba Pb

= = = =

20 43.75 68.5 103.5

4 4 4 4

In these tables Dumas not only stated complex numerical relationships but also implied a convertibility of the elements. For example, according to his equations, chlorine may actually be composed of fluorine--the basic member of the halogen family--to which has been added a quantity of atomic material; bromine and iodine result from additional increments of the material. For several years, Dumas had already hinted at the possibility of chemical convertibility, a notion he derived from Prout's hypothesis, first advanced in 1815. Using rather inadequate atomic weight determinations, Prout had attempted to show t h a t the atomic weights of the various elements are exact multiples of the weight of hydrogen, his hypothesis being t h a t these elements are all composites of hydrogen--the ' primary matter ' While m a n y chemists found a certain appeal in Prout's hypothesis, it was not generally accepted. As for Dumas, he began to give credence to Prout in 1840 while engaged in exhaustive atomic weight determinations of carbon, in which he found its empirical weight to be an exact multiple of that of hydrogen (H = 1.00; C = 12.00). Upon examining the accepted weights of other elements, Dumas observed t h a t although not all were exact multiples of hydrogen--that is, whole numbers--many of the exceptions were strikingly close to being either quarter- or half-numbers. In his articles on numerical relationships, he listed twenty-two elements os having atomic weights of whole numbers (Br--80, Ag=108, etc.), eight as half-numbers (Mg=27.5, C1=35.5, etc), and five as quarternumbers (A1--13.75, Zn=32.75, etc.). This amounted to an extension of Prout's hypothesis, the weights being multiples of either the whole, half-, or quarter-weight of hydrogen. Thus, although Dumas rejected the notion of triads, he revived another fascinating but unsubstantiated concept in his intricate assumption of a ' primary matter '

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D u m a s b y no m e a n s settled the question o f the relationship of the elements. H i s speculations b r o u g h t a swift r e s p o n s e f r o m Max y o n P e t t e n k o f e r in Munich, who later gained i n t e r n a t i o n a l r e n o w n for his application o f c h e m i s t r y to the field of hygiene b u t who a t this t i m e was concerned w i t h the t h e o r e t i c a l p r o b l e m of chemical combination. 1= Like D u m a s , he r e j e c t e d the notion o f triads, s t a t i n g t h a t t h e n u m e r i c a l relationships f o u n d in t h e m were o n l y coincidental. While t h e a t o m i c (or equivalent) weight o f t h e middle m e m b e r o f t h e analogous e l e m e n t s chlorine-bromine-iodine was indeed t h e m e a n of t h e o t h e r two, P e t t e n kofer n o t e d t h a t the a t o m i c weight of t h e middle m e m b e r o f fluorinechlorine-bromine, e l e m e n t s j u s t as analogous as t h o s e in the o t h e r triad, was not t h e m e a n of the o t h e r two. The s a m e d i s c r e p a n c y held if one grouped magnesium-calcium-strontium, instead of calcium-strontiumbarium. B u t P e t t e n k o f e r also r e j e c t e d Dumas's s y s t e m for being too complex. I n its place he s u b s t i t u t e d a scheme o f his own, which d i s p l a y e d a g r e a t e r r e g u l a r i t y o f weights within groups of elements. Differences in equivalent weights, he m a i n t a i n e d , were usually multiples o f 8, although somet i m e s of 5, 18, or 22. T h u s :

Li Na K Mg Ca Sr Ba 0 S Se To Hg Ag

= 7 -- 23 = 39 = 12 = 20 = 44 = 68 -- 8 = 16 = 40 = 64 = 100 =108

16=8x2 16=8x2

C B Si N 1) As Sb Cr Mo V W

= 6 =11 =21 = 14 = 32 = 75 =129 = 26 --48 =70 =92

5=5xl 10=5x2

8=8xl 24=8x3 24=8x3

ls=18x

]=[(2x5)+S]x ] [blank] la 54=18 3=[(2 x 5)+S] x 3

8=8xl 24 = 8 x 3 24 = 8 x 3

22 22 22

8=8x1

,2 A n n . der Chem. u n d P h a r m . , 1858, 105, 187-202. la P e t t e n k o f e r offered no e x p l a n a t i o n for t h e i n c r e m e n t b e t w e e n p h o s p h o r u s a n d arsenic being 43 a n d , therefore, n o t fitting his s c h e m e ; he s i m p l y s t a t e d t h a t t h i s g r o u p of four e l e m e n t s is divided into t w o sections of n a t u r a l l y paired e l e m e n t s .

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Although Pettenkoffer claimed that his system was simpler than that of Dumas, it was still based on the same line of reasoning---regular increments--and had little advantage over it.
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Evaluation of Mendeleev's Precursors. In reviewing the work of these men, one finds that despite their lively interest in the numerical relationship of the elements during the 1850s and early 1860s, they only partially realized their hopes for systematization and did not discover an underlying principle. In each case the intrigue of numbers led these investigators to seek more precise and aesthetically satisfying relationships than their data could support. Not only did the apparent significance of DSbereiner's triads prove misleading, but Dumas's acceptance of the notion of primary matter and his attempt to uphold Prout's hypothesis introduced an additional fallacy. Compounded b y the prevailing ambiguity over the meaning and usage of atomic weights versus equivalent weights, these accumulative biases tended to obscure the principle so diligently sought. Nevertheless, these inadequacies should not be exaggerated. With only partial data and a limited reservoir of theory, these chemists were probing a difficult field of chemical interpretation. Despite their fallacious leads, they did correctly portend the classification of the elements, particularly as Lenssen endeavoured to include all of the elements in a single system and both Kremers and Dumas took the faltering but highly significant step of attempting to establish relationships not only within groups of analogous elements but between dissimilar groups. Although these chemists fell short of finding a satisfactory solution to the problem of relationships, they accentuated the presentiments that both a system and a principle existed, thus providing an incentive for further work by others, including ~[endeleev. Mendeleev's Interest in the Problem ~[endeleev's work on the relationship of the elements derived from both theoretical and practical concerns. Not long after accepting the chair of inorganic chemistry at St. Petersburg University in 1865, the young chemist set to work writing a textbook on this subject, his famous Fundamentals of Chemistry (Osnovy/chimii). At the end of 1868, he had completed the first volume, which dealt with general questions of chemistry, as well as certain common elements: hydrogen, oxygen, nitrogen, and the halogens; and he had begun the second volume, devoting the first two chapters to the alkali metals. 13 At this point he faced the decision of how
14 D. I. Mendeleev, Sochineniia, Leningrad-Moscow, 1934-1956, 25 vols., vol. xiv, p. 6. Volumes 13 a n d 14 are r e p r i n t s of P a r t s I a n d I I of Osnovy khimii.

4.

5.

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19]

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to organize the remaining material, particularly the order in which to discuss the rest of the elements. This practical problem had important theoretical ramifications, as Mendeleev realized, for whatever system he might devise needed a rationale to support it; and if the system were to include all of the elements, it must involve a universal principle. As Mendeleev pondered the problem, he consulted the investigations of Gladstone, Kremers, Lenssen, Dumas, and Pettenkofer, and like them he surmised t h a t the elements were related numerically according to their atomic weights. But unlike them he did not subscribe to the notion of triads or of a unified system of elements based on composites of ' primary matter '. In order to explain this reluctance, one must consider Mendeleev's attention to the persuasive work of the Belgian chemist, Jean-Servais Stas, who, by the mid-1860s, had discredited both of these notions. While professor of chemistry at the Royal Military School in Brussels, Stas engaged in an extended project to determine more precisely than even had Berzelius (whose tables were then widely accepted) the atomic weights of a number of common elements. In ]860, Stas published the results of over a decade of rigorous experimentation, which showed t h a t for the halogens and alkali metals, as well as nitrogen, sulphur, lead, and silver, the atomic weights were neither whole numbers nor even multiples of one-half or one-fourth, as Dumas maintained. In his conclusions, Stas specifically refuted Prout's hypothesis that all elements were composites of a primary matter. 15 When the Swiss chemist Charles Marignac, in an a t t e m p t to uphold Prout's hypothesis, challenged Stas's work on the grounds t h a t he had not demonstrated the constancy of the atomic weights of these elements in different chemical combinations --for example, the ratio of silver to chlorine might be different in AgC1 than in AgC1Od--Stas spent several additional years proving that indeed the atomic weight of each element was constant. With cve]x more precise values, he again refuted Prout's hypothesis, showing t h a t if H = 1.000, then: N = 14.009 Li = 7.004 Na = 22.980 K = 39.O4O C1 Br I Ag
208-336.

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35.368 79.750 126.533 107-660

is Bull. Acad. sci. lettres et beaux-arts de Belgique (Classe des sciences), 1860, 10,

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The publication of these results in 186616 convinced all but a few diehards t h a t Prout's hypothesis was unsound. Mendeleev acknowledged the excellent quality of Stas's work in the first edition of Fundamentals of Chemistry, agreeing t h a t Prout's hypothesis was untenable, as were Dumas's one-half and one-quarter atomic weights. 17 Stas's investigation also tended to discredit the notion of the triads, inasmuch as those who employed them relied on approximate values, generally rounded off to integers. However, this was not the question to which Stas explicitly addressed himself, nor did Mendeleev reject the triads solely because of Stas's work. He also recognized t h a t when the triads were extended to include all of the elements, as in Lenssen's system, t h e y resulted in extremely unnatural groupings according to their properties. It is true t h a t Mendeleev did refer to triads in the first volume of Fundamentals of Chemistry and the initial chapters oi the second volume, written before his discovery of the Periodic Law: he noted that the atomic weight of sodium was the mean of lithium and potassium, as well as t h a t bromine was the mean of chlorine and iodine. But he indicated t h a t he did this in order to show parallels between groups of elements, not to designate triads within groups; and he did not pursue the notion of the triads. In fact, he suggested t h a t the newly discovered elements of rubidium (1861), caesium (1860), and thallium (1861) belonged to the alkali metal group, just as fluorine belonged to the halogens, in both cases extending the groups to more t h a n three members, is Thus, by the time ~Iendeleev began to work intensively on the problem of classification, he had discarded any lingering notions of either triads or primary matter, notions t h a t had so seriously encumbered his precursors. Free from these biases, Mendeleev also took advantage of other developments in chemical theory in the 1860s, particularly in regard to a clearer definition of atomic weights. As long as confusion over the distinction between atomic weights and equivalent weights continued, he could never have devised a system of relationships based on a single sequence of elements, let alone a periodic sequence. For example, as long as calcium was used according to its equivalent weight of 20 instead of its atomic weight of 40, it could not follow potassium, whose atomic, as well as equivalent, weight was 39. However, during the 1860s, Mendeleev, along with many other chemists, converted to a defined and consistent use of atomic weights.
1, A n n . de chem. et de phys., 1866, 99 215-243. IT Mendeleev, Sochineniia, vol. xiv, p. 245. is Ibid., vol. xiii, p. 758; vo]. xiv, p. 53. L a t e r , in his article a n n o u n c i n g his d i s c o v e r y of t h e Periodic L a w , M e n d e l e e v c o m m e n t e d t h a t one of t h e m a j o r flaws in L e n s s e n ' s s y s t e m r e s u l t e d f r o m his a t t e m p t to e s t a b l i s h t r i a d s , t h e r e s u l t b e i n g t h e artificiality of t h e s y s t e m . Zhurna[ russkago fiziko-khimieheskago obshchestva, 1869, 19 60-77.

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This conversion occurred gradually. In writing his undergraduate thesis at the Pedagogical Institute in St. Petersburg during 1855-1856, Mendeleev employed atomic weights based on Berzelius's tables; 19 a few months later, for his master's thesis, he adopted the atomic weights proposed by the French chemist Charles Gerhardt, who halved many of Berzelius's values, thus correcting those for such elements as potassium, silver, and chlorine (which Berzelius had erroneously listed at twice their actual weight), but wrongly altering the already correct values for such elements as calcium, copper, and zinc. s~ Undergraduate thesis 78.2 216.0 71.0 40.1 63.4 65.0 Master's thesis 39.1 108.0 35.5 20.0 31.7 32.6

K Ag C1 Ca Cu Zn

In neither case did Mendeleev distinguish adequately between atomic and equivalent weights, nor did he do so in his first published article in 1858. In fact, in this article he extended the erroneous features of Gerhardt's system b y halving even the values for oxygen and carbon, which resulted in such formulae as H~O 2 for water and C12H~ for benzene. ~1 He realized that these values were unsatisfactory and soon abandoned them, especially because of his introduction to a more logical system of atomic weights after 1860. In that year, while studying on a fellowship at the University of Heidelberg, he took time to attend the important Karlsruhe Congress, at which some 140 prominent chemists from throughout Europe attempted to reach a general agreement on the definitions of atomic weights, equivalents, and related terms. In a letter to his friend and former teacher in St. Petersburg, A. A. Voskresenskii, he related that he was much impressed by Stanislao Cannizzaro's plea for adopting atomic weights based consistently on vapour densities (according to Avagadro's hypothesis) rather than on combining weights, which seemed to have caused so much confusion. As he enthusiastically commented, Cannizzaro exposed the flaw in Gerhardt's system, which had at first appeared to be such an improvement on Berzelius's values.
lgMendeleev, Periodicheskii zakou, 621-624. 2o Ibid., 646-650. 21 Mdlanges physiques et chimiques tirds du Bulletin de l'Acaddmle impdriale des s~iences de St.-Petersbourg, 1856-1859, 3, 402-428.

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According to Carmizzaro the atomic weights of the elements listed in the table above would be: ~ K 39 Ag 108 C1 35.5 Ca Cu Zn 40 63 65.5 ~like Gerhardt ) ~ unlike Gerhardt

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As receptive as was Mendeleev to Cannizzaro's persuasive argument, there is evidence that several more years passed before he thoroughly converted to a consistent use of atomic weights. Among Mendeleev's papers was found a series of lecture notes, which include a list of 63 elements and their weights. Although this list is undated, one can conclude by comparing the weights Mendeleev used in it with those t h a t had been established at various points during the 1860s, particularly for recently discovered elements, t h a t he wrote it in either 1864 or 1865. In the list, he used equivalent weights for some 13 of the elements. Even for calcium, for which he had used the atomic weight of 40 in his letter following the Karlsruhe congress, he now reverted to the equivalent weight of 20. ~a However, in the first volume of Principles of Chemistry, written in 1868--several months before his work on the Periodic L a w - he included a list of 22 common elements (including calcium), for which he used atomic weights throughout. 24 Thus, by the time he began to work seriously on the problem of classifying the elements, he was already using their atomic weights consistently--an impertant prerequisite to his discovery of the Periodic Law.

6. Recognition of the Law


What, then, was the final process by which Mendeleev arrived at the crucial point of discovery--his recognition of periodicity? In
22 Mendeleev, Periodictteskii zakon, 663-665. ~a B. M. Ke(lrov, Den' odnogo velikogo otkrytlia, Moscow, 1958, 341. K e d r o v d a t e s the list as 1867 or 1868, b u t this is p r o b a b l y too late, because Mendeleev included no weight t h a t h a d been established or revised after 1865, whereas he did use values t h a t h a d n o t been established until 1864. F o r example, he listed i n d i u m as 37, the weight its discoverers, F e r d i n a n d Reich and Theodor Richter, r e p o r t e d in Journal fiir praktische Chemic in 1864; however, in an article in this journal in 1865, Clemens Winkler revised the weight to 35.9 a n d in 1867 to 37.8. Mendeleev evidently was familiar w i t h these changes, because he used the 1867 value for his Periodic Table (actually he doubled this equivalent weight to its atomic weight of 75.6). Similarly, for o t h e r e l e m e n t s - - y t t r i u m , e r b i u m a n d niobium - - M e n d e l e e v did n o t use weights reported after 1864 or 1865 in his lecture list. 24 Mendeleev, Sochineniia, vol. xiii, p. 342. In this list Mendeleev did state the weight of c a r b o n as 6 - - i t s equivalent w e i g h t - - b u t this a p p a r e n t l y w a s an oversight, because on the following page he calculated the weight of Na2CO a as 106, which required carbon to be 12, its atomic weight.

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his initial article announcing the discovery, he described his methodology but briefly and vaguely. He wrote t h a t he 'selected the bodies with the smallest atomic weights and arranged them according to the magnitude of their atomic weights. In so doing, it appeared that there exists a periodicity of properties of the simple bodies, and even that according to valency the elements follow one another in the order of an arithmetric sequence of the magnitude of their atomic weights.' He added that he then proceeded to bring all of the elements into a system based oft this principle. 25 While indicating that Mendeleev listed the simpler elements sequentially according to their increasing atomic weights, this description does not at all explain how such an arrangement enabled him to recognize the periodicity of their properties. Nevertheless, his idea of arranging the elements in a single sequence became the generally accepted interpretation of the process of his discovery. Moreover, other fragments of evidence seemed to support and amplify this view. One of his friends, the Czech chemist Bohuslav Brauner, related shortly after Mendeleev's death in 1907 t h a t Mendeleev once told him how he had written the symbols and atomic weights of the elements on individual cards and arranged them in various ways, none of them satisfactory until he placed them one after another according to their increasing atomic weights. Having arranged the following elements in a row: H=I Li=7 Be=9 B=ll C=12 N = 1 4 0 = 1 6 F = 1 9 , he found t h a t the elements immediately following would form a second row directly below the first: N a = 2 3 Mg=24 A1=27 Si=28 P = 3 1 S = 3 2 C1=35.5, each element having properties similar to the element above it, and that these properties were repeated in successive rows of the elements arranged according to their increasing atomic weights. 26 While the simplicity of this explanation has its appeal, recently published archival materials, when studied carefully, disclose t h a t the discovery probably resulted from a different process. Rather than listing a single sequence of elements, Mendeleev compared the atomic weights of various groups of elements, gradually accumulating a sufficient number to enable him to recognize their periodicity. The first of these materials is some notes written on the back of a letter to Mendeleev from A. I. Khodnev, secretary of the Free Economic
25Z h u r n a l russ~sago fizilco.]chimiches]cago obshchestva, 1869, 1~ 60-77. 26 Collection of Czechoslovak Chemical Communications, 1930, 2, 225. The R u s s i a n chemist, V. In. K u r b a t o v , also briefly relates in his memoirs t h a t Mendeleev once told him h o w he wrote the properties of the elements on cards, a r r a n g e d t h e m according to these properties, and arrived at a table. A . A . Makarenia and I. N. Filimonova (eds.), D. I. Mendeleev v vospominaniiakh sovremennikov, Moscow, 1969, 107.

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Society in St. Petersburg, inquiring about Mendeleev's preparations to inspect some cheese-processing plants for the Society. ~7 The letter is dated 17 February, 1869, and judging from the note of urgency in its message, it was probably delivered by messenger t h a t day. After jotting down the symbols for several elements on the back of the letter, the purpose of which is not apparent, Mendeleev made the following calculations: (7) (16) 23 14 9 7 39 24 15 12 85 65 20 32 133 112 21 56

(The figures 14 and 9 in the first column were written over 7 and 16, respectively.) Evidently, Mendeleev was comparing the atomic weights of the following two groups of elements: Na [Be?] ~s K Mg Rb Zn Cs Cd

Mendeleev's purpose in choosing these two groups of elements was logical and practical. Having just finished the chapters on the alkali metals for his textbook, he was contemplating t h a t on the basis of chemical properties, as well as valency, the analogues of zinc might well follow the alkali metals, even before the alkaline earths. This arrangement accorded with one of the currently accepted concepts t h a t the analogues of zinc formed an intermediate group between the alkali metals and the alkaline earths. Indeed, in his initial article on the Periodic Law, he referred to Kremer's arrangement of these three groups: 29 Li Mg Ca Sr Na Zn Ba K Cd

~ K e d r o v (note 23), 42. 2s I t is difficult to k n o w w h i c h e l e m e n t M e n d e l e e v i n t e n d e d b y t h e figure ' 7 ': l i t h i u m , w h o s e a t o m i c / e q u i v a l e n t w e i g h t h a d b e e n e s t a b l i s h e d a t t h a t value, or beryllium, w h o s e e q u i v a l e n t w e i g h t h a d n o t y e t been decided as 4.7 (if its oxide w a s BeO) or 7.0 (if Be2Oa). See Jahresbericht iiber die Fortschritte der Chemie, 1868, x x x i . O n e m i g h t well c o n j e c t u r e t h a t M e n d e l e e v h a s t i l y chose Be 7, e v e n t h o u g h t h i s m e a n t t h a t Be m u s t be t r i v a l e n t a n d w o u l d n o t c o r r e s p o n d to t h e b i v a l e n t Mg-Zn-Cd. T h a t he m i g h t h a v e e r r e d in t h i s r e s p e c t is i n d i c a t e d b y t h e fact t h a t in t h e r u d i m e n t a r y t a b l e s following t h e s e initial calc u l a t i o n s (see F i g u r e s 1 a n d 2), M e n d e l e e v w a s u n d e c i d e d a b o u t Be, b o t h in r e g a r d to its w e i g h t a n d v a l e n c y . F u r t h e r m o r e , since he e v e n t u a l l y placed Be w i t h M g - Z n - C d (see Figg u r e s 3 a n d 4), albeit as a b i v a l e n t e l e m e n t h a v i n g t h e a t o m i c w e i g h t of 9.4 ( t h a t is, 2 x 4-7), he p r o b a b l y h a d t h i s association in m i n d in t h e initial calculations. I n a n y e v e n t , t h e t h e significance of t h e figure ' 7 ' is n o t t h e k e y to t h e significance of t h e s e calculations, a s e x p l a i n e d in t h e discussion below. 29 Z h u r n a l russkagofiziko-khimicheskago obshchestva, 1869, 1, 60-77. See t h e d i s c u s s i o n of K r e m e r ' s i n v e s t i g a t i o n above.

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With this scheme in mind as he wrote on the back of Khodnev's letter, Mendeleev calculated in the third row of figures the difference in each pair of atomic weights, probably in order to determine if there existed a regular rate of increase. Upon finding that the difference in the first column--16--was larger than that in the second column--15--Mendeleev doubled the value being subtracted in the first column, correcting it from the equivalent weight to the atomic weight of beryllium a~ and giving a new difference of 9. Still this did not provide a logical sequence of differences, and Mendeleev revised the values for the analogues of zinc in the fourth row of figures by changing 14 back to 7 and halving the values for the other elements from the second row--actually giving them their equivalent weights. This afterthought proved no more instructive than Mendeleev's first calculation, and he pursued it no further. However, the comparison that he had made was extremely important, for it was the beginning of the process that led to his recognition of the Periodic Law. He had compared the atomic weights of two dissimilar groups of elements, whereas, as one recalls, his precursors had almost wholly limited their comparisons to analogous elements, the exceptions having been Kremers with his ' conjugated triads ' and Dumas with his incremental formulae. In his arrangement of the alkali metals, zinc analogues, and alkaline earths, cited above, Kremers may not consciously have been comparing dissimilar elements, but as Mendeleev repeated this arrangement, he apparently realized, as we shall see, the importance of comparing additional dissimilar groups. The notes on Khodnev's letter indicate Mendeleev's first breakthrough. The second manuscript adding to our knowledge of N[endeleev's recognition of the Periodic Law is a sheet of paper found glued inside a book in Mendeleev's personal library, dated 17 February, ]869, on which he had written two tables of elements and their atomic weights. 31 Both tables contain only part of the elements, but they show how he was proceeding with his comparisons of dissimilar groups of elements. As one can see from the configuration of the first table (Figure 1) he probably wrote it in stages. Judging from the regularity of their rows and columns, he wrote the F, 0, N, and C groups first. This was not a direct continuation of his previous comparison of the alkali metals and the analogues of zinc, but it was a logical step if one surmises that he indeed had decided to pursue the comparison of dissimilar groups. It also reflects the pattern of Mendeleev's thought processes: at this point he apparently was beginning to detect the link between two separate sets of relationships--a
80 See n o t e 28. 31 K e d r o v (note 23), p. 49. I n rega.rd to t h e s e t a b l e s , I t e n d t o a g r e e w i t h K e d r o v ' s a n a l y s i s a n d follow a line of r e a s o n i n g s i m i l a r to his. A.S. o

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kind of 'bisociation ,.a2 The first relationship was that of analogous elements within groups--the analogues of F, 0, N, and C, respectively-whose atomic weights increased continually, if not b y constant increments. The second relationship was that of F, 0, N, and C, themselves. On the basis of their properties as non-metals and their regularly changing valency from 1 to 4, Mendeleev could detect this relationship readily; and he could also notice that their atomic weights increased correspondingly. Already he had suspected the efficacy of comparing dissimilar elements; now, as he listed entire groups side by side, he could perceive their bi-directional relationships. Through this 'bisociation' he recognized that he could integrate these sets of relationships into a single system. A striking realization, to be sure: a genuine act of creativity. Yet, the apparent synthesis was not at this point conclusive; and ~endeleev immediately set about extending the relationships. To this nucleus of elements, he added several other groups: the alkaline earths on top and the alkali metals, analogues of zinc, and several other elements at the bottom. Altogether six groups fitted together admirably--two others not so well. On the bottom half of the sheet of paper, Mendeleev rearranged and expanded the table even further (Figure 2). Significantly he placed the alkaline earths, rather than the analogues of zinc, next to the alkaline metals. This solved the original practical problem of which elements to include next in his textbook, but far more important it constitutes the concluding stage in the process o f ' bisociation '. From the configuration of the table it appears that as Mendeleev wrote down the six groups-alkaline earths, alkali metals, F, 0, N, and C--he did so not horizontally by groups, but vertically, each column in sequence, indicating that by this time he surely recognized their bidirectional relationships. He had achieved the crucial synthesis: in recognizing the repetitive relationship of properties and atomic weights, Mendeleev had arrived at the principle of periodicity. Having constructed 'this much of a table, he then proceeded to add several other elements which fitted readily. In all, he included 42 elements, some two-thirds of the total known. It remained then for Mendeleev to expand his table to include all of the elements. Quite possibly at this time he used the cards to which Brauner referred. The remaining elements were far less investigated than those he had already arranged, and although he undoubtedly understood by this time that they should be included according to their atomic weights, he still needed to determine exactly where they should fit along the periphery. The resulting arrangement appears in the third manuscript, Mendeleev's first draft of a table comprising all of the known elements (Figure 3). aa
32 A r t h u r K o e s t l e r ' s t e r m in The Act of Creation, L o n d o n , 1964, 656-660. aa Mendeleev, Periodicheskil zakon, 8.

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~4 Ibid.

The Process of Discovery: Mendeleev and the Periodic Law

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printer. It served as the form of the table Mendeleev included in his article on the discovery of the Periodic Law. a5

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7. Confirmation 'The confirmation of a law', wrote Mendeleev, 'is possible only by deducing consequences from it, which would be impossible and unexpected without it, and by justifying those consequences by experimental proof '.~
In the case of the Periodic Law, confirmation resulted as other chemists verified various predictions Mendeleev made regarding the existence and characteristics of several undiscovered elements, as well as corrections in the atomic weights of certain elements already known but inadequately studied. In his table he left several blank spaces, in which he placed question marks, along with the approximate atomic weights of elements lleeded to fill these gaps. For example, he suggested two elements, one similar to aluminum, the other to silicon, which would have atomic weights between 65 and 75. I a 1871, he provided the names ' eka-aluminum ' and ' eka-silieon' for these anticipated elements, and he added ' eka-boron' for an element needed to fill a gap which appeared in a slightly revised version of the table. 37 In verification of his predictions, all three of his eka-elements had been discovered by 1885, each having approximately the properties and atomic weight he had specified. ~s Predicted atomic weight eka-aluminium 68 eka-silicon 72 eka-boron 44 Discovered atomic weight gallium 69.9 germanium 72.32 scandium 44.1

Apparently even l~endeleev had not expected such rapid confirmation, for he later admitted: ' When in 1871 I wrote an article or~ the application of the Periodic Law to the determinatiorl of the properties of as yet undiscovered
a~ Note t h a t in b o t h drafts of the table seven e l e m e n t s , - - E r , Yt, In, Ce, La, Di, a n d T h - - d o not fit properly. The first three, whose atomic weights are listed between 57 a n d 75, Mendeleev placed between elements having weights of 40 a n d 50; the other four, whose atomic weights range from 92 to 118, fall between elements h a v i n g weights of 87 a n d 90. Mendeleev simply left these elements in the margin, unplaced ; in later years, w h e n corrected atomic weights were established for them, Mendeleev incorporated t h e m into the table. a6 Mendelecv, Periodicheskii zakon, 323, from Osnovy khimii, 8th edition. 87 Ibid., 150-153, reprint of Russian draft of an article in Annalen der Chemic und Pkarmacie, 1871, Supplement VIII, 133-229. a8 W h e n Leeoq de Boisbaudran announced the discovery of gallium, he reported its density as 4.7, considerably lower t h a n Mendeleev's prediction of 5.9. More accurate m e a s u r e m e n t proved Mendeleev correct. Comptes Rendus, 1875, 81, 969-972; 1876, 82, 1036-1039.

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elements, I did not think I would live until this consequence of the Periodic Law was verified; but reality turned out otherwise '

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The discoverers of the eke-elements Mendeleev acknowledged as the ' t r u e corroborators' of the Periodic Law. a9 In addition to these gaps for undiscovered elements, Mendeleev made other predictions, most---but not all--of which were fulfilled. To the elements E r = 56, Y t = 60, and I n = 75.6, which Mendeleev could not satisfactorily incorporate into his original table, he assigned new atomic weights in 1871 (actually higher multiples of their equivalent weights than accepted in 1869) and placed them in positions consistent with their properties: In--113 between Cd=112 and S n = l l 8 ; Y t = 8 8 between Sr = 87 and Z r = 90; and Er-- 178 in the midst of several blank spaces still to be filled. Subsequent atomic weight determinations proved Mendeleev correct in his predictions for indium and yttrium, their weights being 114.8 and 88.9; erbium, however, was shown to have an atomic weigh~ of 167.27 and belong to the rare earth series, a group whose members, except for erbium and cerium, were unknown at the time Mendeleev made his predictions.4~ As scientists learned more about atomic structure, they modified Mendeleev's fundamental explanation of the periodic relationship of the elements, particularly by concluding t h a t the periodic arrangement of the elements is actually not a function of their atomic weight but of their atomic number. However, in most cases, an increase in atomic number entails a corresponding increase in atomic weight, which means t h a t although Mendeleev's explanation had a somewhat incorrect theoretical basis, it nevertheless disclosed a periodic relationship of the elements based on a genuine law of nature. Thus, from presentiments to recognition to confirmation, the discovery of the law was complete.

a9 Mendeleev, Periodicheskii zakon, 323-324, from Osnovy khimii, 8th edition. In his 1871 article, Mendeleev also suggested the possibility of eka-caesium [175], dvi-caesium [220], eke-niobium [146], eka-tantalium [235], eke-manganese [100], and tri-manganese [190]. His prediction of eka-manganese approximated technetium [99], discovered in 1939; but his other predictions proved inaccurate, primarily because he could not foresee that eventually the lanthanide and actinide series would become a p a r t of the system of elements. 40 I n his system Mendeleev also questioned the currently accepted atomic weight of gold, since platinum, iridium, osmium, and mercury, all of which he was convinced must come before gold, had been assigned higher atomic weights. Additional atomic weight determinations showed t h a t actually the weights of platinum, iridium, and osmium were incorrect--their revised values permitted them to remain before gold, as Mendeleev had placed them. I n later tables the positions of gold and mercury were exchanged, placing them in different groups than before on the basis of their properties and in the proper sequence according to their atomic weights.