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Harold C. Urey (1893-1981), FG Brickwedde (1903-1989), GM & Murphy (1903-1968)


Ein Wasserstoff-Isotope der Masse 2
Physical Review 39, 164-165 (1932).
Copyright 1932 von der American Physical Society, reproduziert mit Erlaubnis.
Das Proton-Elektron-Grundstück von bekannten Atomkerne zeigt einige ziemlich starke
Regelmäßigkeiten zwischen Atomen niedriger Ordnungszahl. [1] Bis zu einem einfachen Schritt O16-
weise Figur erscheint, in die die nukleare Arten H2, H3 und He4 könnte sehr gut ausgestattet. Birge
und Menzel [2] haben gezeigt, dass die Diskrepanz zwischen der chemischen Atomgewicht des
Wasserstoffs und Aston Wert durch die Masse Spektrographen durch die Annahme einer Wasserstoff-
Isotop der Masse 2 zeigen das Ausmaß der 1 Teil in 4500 Teile werden könnte entfielen Wasserstoff der
Masse 1.
Es ist möglich, mit Zuversicht die Berechnung der Dampfdrücke der reinen Stoffe H1H1, H1H2,
H1H3, im Gleichgewicht mit dem reinen festen Phasen. Es ist nur notwendig, anzunehmen, dass in der
Debye-Theorie der Festkörper-, θ umgekehrt proportional zur Quadratwurzel der Massen dieser
Moleküle und die Rotations-und Schwingungs-Energie der Moleküle nicht in den Prozess der
Verdampfung zu ändern. Diese Annahmen werden in Übereinstimmung mit etablierten experimentellen
Beweis. Wir finden, dass die Dampfdrücke für diese Moleküle im Gleichgewicht mit den Feststoffen in
das Verhältnis von p11: p12: p13 = 1:0.37:0.29 werden sollte. Die Theorie der flüssigen Zustand ist
nicht so verstanden vell, aber es scheint vernünftig zu glauben, dass die Unterschiede in der
Dampfdruck dieser Moleküle im Gleichgewicht mit ihren whould Flüssigkeiten recht groß zu sein und
sollte es ermöglichen, eine rasche Konzentration der schwereren Isotopen, wenn sie vorhanden sind im
Rückstand aus der einfachen Verdampfung von flüssigem Wasserstoff in der Nähe der Tripelpunkt.
Dementsprechend sind zwei Proben wurden durch Verdampfen von Wasserstoff große Mengen von
flüssigem Wasserstoff und sammeln das Gas, das aus dem letzten Teil der letzten Kubikzentimeter
eingedampft vorbereitet. Die erste Probe wurde aus dem Endabschnitt von sechs Liter Flüssigkeit bei
Atmosphärendruck verdampft gesammelt, und die zweite Probe aus vier Liter bei einem Druck
verdampft nur wenige Millimeter über dem Tripelpunkt. Der Prozess der Verflüssigung hat
wahrscheinlich keine Wirkung auf die Veränderung der Konzentration der Isotope, da keine merkliche
Änderung wurde in der Probe verdampft beobachtet bei atmosphärischem Druck.
Diese Proben wurden für die Atom-Spektren von H2 und H3 in einer Wasserstoff-Entladungsrohr in
Holz so genannten "Black Stage" mit dem zweiten Ordnung eines 21 Fuß-Gitter mit einer Dispersion
von 1,31 Å pro mm ausgeführt werden untersucht. Mit der Probe verdampft bei Siedetemperatur keine
Konzentration so hoch geschätzt worden war festgestellt worden war. Dann stiegen die Forderungen, so
dass das Verhältnis der Zeit der Exposition gegenüber dem Mindestmaß, um die H1-Linien auf unseren
Tellern dich über 4500:1 war. Unter diesen Bedingungen fanden wir in diesem Beispiel als auch in
normalen Wasserstoff schwache Linien auf der berechneten Positionen für die Linien H2 begleitenden
Hβ, Hγ, Hδ. Diese Zeilen müssen allerdings nicht in der Wellenlänge mit einer molekularen Linien
stimmen in der Literatur berichtet. [3] Allerdings waren sie so schwach, dass es schwierig war, sicher
sein, dass sie nicht die Geister der stark überbelichtet Atomlinien.
Die Probe von Wasserstoff in der Nähe der Tripelpunkt verdampft zeigt diese Linien stark verbessert,
bezogen auf die Linien des H1, sowohl über die gewöhnlicher Wasserstoff-und der ersten Probe. Die
relativen Intensitäten kann durch die Anzahl und Intensität der symmetrischen Geister auf die Platten
gerichtet werden. Die Wellenlängen der H2-Linien, die auf diesen Platten leicht innerhalb von ca. 0,02
A gemessen werden. Die folgende Tabelle gibt den Mittelwert der beobachteten Verschiebungen dieser
Linien von denen der H1 und der berechneten Verschiebungen:
Line



Δλ calc.
1,793
1,326
1,185
1,119

Δλ obs.

Ordentliche Wasserstoff
--
1,346
1,206
1,145

1. Stichprobe
--
1,330
1,119
1,103

2. Probe
1,820
1,315
1,176
--

Die H2-Linien sind breit, wie es zu einer engen ungelöste Dubletten zu erwarten, aber sie sind nicht so
breit und diffus wie die H1 Linien wahrscheinlich aufgrund der geringeren Dopplerverbreiterung.
Obwohl ihre relativen Intensitäten, um die Geister der jeweiligen H1 Linien erscheinen nahezu
konstant für eine Probe von Wasserstoff, sind sie nicht für ihre Geister Intensitäten im Vergleich zu den
bekannten Geister für ihre Intensitäten sind nicht dasselbe im Falle des gewöhnlichen Wasserstoffs und
des 1. Stichprobe, wie sie im Falle der zweiten Probe. Sie sind nicht molekularen Linien für sie nicht
auf einer Platte mit dem Entladungsrohr in der "weißen Stadium" mit den molekularen Spektrum
erweitert (H2γ getroffen wurde, als eine leichte Unregelmäßigkeit auf einem Mikrophotometer Kurve
von dieser Platte zu finden). Schließlich die H2α Zeile ist in ein Wams mit einem Abstand von etwa
0,16 Å im Einvernehmen mit den beobachteten Trennung der H1α Linie gelöst.
Die relative Häufigkeit in gewöhnlichem Wasserstoff zu urteilen aus der relativen Minimierung der
Exposition beträgt etwa 1:4000, oder weniger, im Einvernehmen mit Birge und Menzel schätzt. Eine
ähnliche Schätzung der Zahl in der zweiten Probe angegeben einer Konzentration von etwa 1 in 800.
So eine spürbare Fraktionierung wurde gesichert, als von der Theorie erwartet. [4] keine Beweise für
H3 gesichert ist, aber die Linien würden die Gebiete von unseren Tellern fallen, wenn der Lichthof ist
schlecht.
Die Destillation wurde auf dem Bureau of Standards durchgeführt von einem von uns (FGB), der die
Fortsetzung der Fraktionierung mehr hochkonzentrierten Proben zu sichern. Die spektroskopische
Arbeit wurde an der Columbia University durchgeführt von den beiden anderen (HCU und GMM), die
arbeiten an der molekularen Spektrum.
Harold C. Urey
F. G. Brickwedde
G. M. Murphy
Columbia University,
New York, N. Y.
Bureau of Standards,
Washington, D. C.

5. Dezember 1931.

[1] Urey, J. Am. Chem. Soc. 53, 2872 (1931), Johnston, ibid., 53, 2866 (1931).
[2] Birge und Menzel, Phys. Rev. 37, 1669 (1931).
[3] Gale, Monk und Lee, Astrophys. J. 57, 89 (1928); Finkelnburg, Z. Physik 52, 57 (1928); Connelly,
Proc. Phys. Soc. 42, 28 (1929).
[4] Keesom und van Dijk, Proc. Acad. Sci. Amsterdam 34, 52 (1931).

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Back to the top of Classic Chemie.
SIS SUS
batang
Frederick Soddy (1877-1956)
Intra-Atomladung.

Nature 92, 399-400 (4. Dezember 1913)

Dass die Intra-Atomladung eines Elements wird durch seinen Platz im Periodensystem bestimmt nicht
durch seine Atommasse, wie von A. van der Broek (Nature, 27. November, S. 372) geschlossen, ist
stark von der bisherigen Unterstützung Verallgemeinerungen in Bezug auf die Radio-Elemente und die
periodische Gesetz. Die aufeinander folgenden Vertreibung ein α-und β zwei Teilchen in drei radio-
aktiven Änderungen in beliebiger Reihenfolge bringt die Intra-Atomladung des Elements zurück zu
ihrem ursprünglichen Wert, und das Element wieder in seinen ursprünglichen Platz in der Tabelle,
obwohl seine Atommasse reduziert wird um vier Einheiten. Wir haben vor kurzem erhalten so etwas
wie einen direkten Beweis der Ansicht van der Broek, dass die intra-atomare Ladung des Kerns eines
Atoms ist nicht eine rein positive Ladung, wie auf vorläufige Theorie Rutherford. aber ist der
Unterschied zwischen einer positiven und einer negativen Ladung kleiner.

Fajans, sich in seiner Abhandlung über die periodischen Verallgemeinerung (Physikal. Zeitschr., 1913,
vol. Xiv., S. 131), lenkte die Aufmerksamkeit auf die Tatsache, dass die Veränderungen der chemischen
Natur auf die Ausweisung von α-und β Teilchen daraus genau der gleichen Art wie in der gewöhnlichen
elektrochemischen Veränderungen der Wertigkeit. Er zog daraus den Schluss, dass radio-aktiven

Änderungen müssen in der gleichen Region der atomaren Struktur wie gewöhnliche chemische
Veränderungen, anstatt mit einem ausgeprägten inneren Bereich des Bauwerks oder "Kern auftreten",
wie bisher angenommen. In meinem Vortrag auf der gleichen Verallgemeinerung, dass unmittelbar nach
der Fajans veröffentlicht (Chem. News, 28. Februar), legte ich Wert auf die absolute Identität des
chemischen Eigenschaften der verschiedenen Elemente besetzen den gleichen Platz im
Periodensystem.

Eine einfache Folgerung aus dieser Sicht versorgte mich mit einem Mittel zur Kontrolle der Richtigkeit
der Schlussfolgerung, dass Fajans Radio-Veränderungen und chemischen Veränderungen sind mit der
gleichen Region der atomaren Struktur betroffen. Nach meiner Meinung seiner Schlussfolgerung wäre
nichts anderes, als dass zum Beispiel, Uran in seiner vierwertigen uranous Verbindungen beteiligt sein
müssen chemisch identisch sein mit und nicht trennbar von Thorium-Verbindungen. Bei Uranium-X,
aus Uran ich durch Ausweisung eines α Teilchen gebildet, ist chemisch identisch mit Thorium, wie dies
auch Ionium in der gleichen Weise vom Uran II gebildet. Uran X verliert zwei β Teilchen und geht
zurück in Uran II, chemisch identisch mit Uran. Uranous Salze verlieren auch zwei Elektronen und in
die mehr sechswertiges Uranylverbindungen weiterzugeben. Wenn diese Elektronen aus der gleichen
Region des Atoms uranous Salze kommen sollte chemisch nicht trennbar von Thoriumsalze. Aber sie
sind es nicht.

Es besteht eine starke Ähnlichkeit in der chemischen Charakter zwischen uranous und Thoriumsalze,
und ich fragte Herr Fleck zu prüfen, ob sie auf chemischem Wege trennen könnte, wenn gemischt
werden, wobei das Uran unverändert bleiben überall in der uranous oder vierwertigen Zustand. Herr
Fleck wird die Experimente gesondert bekannt geben, und ich bin ihm zu Dank verpflichtet für das
Ergebnis, dass die zwei Klassen von Verbindungen können leicht durch Fraktionierung getrennt
werden.

Dies, so denke ich, beläuft sich auf ein Beweis dafür, dass die Elektronen als β-Strahlen aus einem
Kern nicht liefern kann Elektronen oder zurückzukaufen, um sie aus dem Ring kommen vertrieben,
obwohl dieser Ring ist zu gewinnen oder zu verlieren Elektronen von außen während der gewöhnlichen
elektrochemischen Veränderungen fähig der Wertigkeit.

Ich halte Ansicht van der Broek, dass die Zahl, die die positive Netto-Ladung des Kerns der Zahl der
der Stelle, die das Element befindet sich im Periodensystem, wenn alle möglichen Orte, von
Wasserstoff bis Uran in der Reihenfolge angeordnet sind, als praktisch erwiesen, so ist Was den
relativen Wert der Ladung für die Mitglieder des Ende der Sequenz, von Thallium, Uran, betroffen ist.
Wir sind im Unklaren gelassen, um den absoluten Wert der Ladung, wegen der Zweifel über die genaue
Zahl der "Seltenen Erden", die es gibt. Wenn wir davon ausgehen, dass all diese bekannt sind, den Wert
für die positive Ladung des Kerns des Uran-Atoms ist etwa 90. Der Erwägung, dass, wenn wir die eher
zweifelhaft Annahme, dass die periodischen fährt regelmäßig zu machen, hinsichtlich der Zahl der
Orte, durch die Selten-Erd-Gruppe, und dass zwischen Barium und Radium, zum Beispiel, zwei
komplette lange Zeit vorhanden ist, wird die Zahl 96. In jedem Fall ist es deutlich weniger als 120, die
Anzahl der Gebühr in Höhe eines halben Atomgewicht, wie es wäre, wenn der Kern der α-Partikel nur
ausgefertigt. Sechs nukleare Elektronen sind dafür bekannt, in der Uran-Atom, das in seiner
Veränderungen sechs β-Strahlen vertreibt existieren. Sind der Kern, der sich aus α Teilchen muss es
dreißig oder vierundzwanzig nuklearen bzw. Elektronen, verglichen mit sechsundneunzig oder 102
bzw. in den Ring. Wenn, wie vorgeschlagen wurde, ist Wasserstoff eine zweite Komponente der
atomaren Struktur, es muss mehr als diese. Aber es kann kein Zweifel, dass es einige werden muss, und
dass die zentrale Ladung des Atoms auf die Theorie Rutherford kann nicht eine reine positive Ladung,
sondern müssen Elektronen enthalten, wie van der Broek abschließt.

Soweit ich persönlich betroffen bin, hat dies in einer großen Klärung meiner Ideen geführt, und es kann
hilfreich sein, andere, obwohl kein Zweifel daran gibt es wenig Originalität in ihm. Das gleiche
algebraische Summe der positiven und negativen Ladungen im Kern, als die arithmetische Summe
unterschiedlich ist, gibt, was ich "Isotope" oder "Isotopen-Elemente" nennen, weil sie den gleichen
Platz im Periodensystem zu besetzen. Sie sind chemisch identisch, und speichern Sie nur im Hinblick
auf die relativ wenigen physikalischen Eigenschaften, die auf Atommasse hängen direkt, auch
körperlich identisch. Unit Veränderungen dieser Kernladung, so algebraisch rechnen, geben die
nachfolgenden Plätze im Periodensystem. Für ein "Ort", oder ein Kernladung, mehr als eine Anzahl
von Elektronen in der äußeren Ring-System bestehen können und in einem solchen Fall das Element
weist variable Wertigkeit. Aber solche Veränderungen der Anzahl oder der Wertigkeit, beziehen sich
nur auf den Ring und externen Umfeld. Es gibt keinen In-und Out-Gehen von Elektronen zwischen
Ring und Kern.

Frederick Soddy
Laboratorium für Physikalische Chemie,
University of Glasgow.
-------------------------------------------------- ------------------------------
Zurück zur Liste der ausgewählten historischen Papieren.
Back to the top of Classic Chemistry.The Streuung von α-und β Teilchen durch Materie und der
Struktur des Atoms
E. Rutherford, F.R.S. *
Philosophical Magazine
Series 6, vol. 21
Mai 1911, S. 669-688

-------------------------------------------------- ------------------------------

669

§ 1. Es ist bekannt, dass die α-und β die Teilchen Ablenkungen leiden unter ihrer geradlinigen Pfaden
durch Begegnungen mit den Atomen der Materie. Diese Streuung ist viel stärker ausgeprägt als für die
β für die α Teilchen wegen der viel kleiner Impuls und Energie der ehemaligen Teilchen. Es scheint
keinen Zweifel daran, dass diese sich schnell bewegenden Teilchen durchlaufen die Atome in den Weg,
und dass die Ablenkungen beobachtet werden durch das starke elektrische Feld im atomaren System
durchlaufen. Es wurde allgemein angenommen, dass die Streuung der ein Büschel von α oder β-
Strahlen beim Durchgang durch eine dünne Platte der Materie das Ergebnis einer Vielzahl von kleinen
Streuungen von den Atomen der Materie durchzogen ist. Die Beobachtungen zeigen jedoch, der Geiger
und Marsden ** über die Streuung von α-Strahlen, dass einige der α Teilchen, etwa 1 in 20.000 bis
einem mittleren Winkel von 90 Grad wurden im Vorbeigehen sich aber eine Schicht aus Gold-Folie
über 0,00004 cm . dick, das entspricht in Anhalten-Macht der α Partikel bis 1,6 Millimeter Luft war.
Geiger *** zeigte später, dass die wahrscheinlichste Winkel der Ablenkung für ein Büschel von α
Teilchen abgelenkt über 90 Grad ist verschwindend klein. Darüber hinaus wird es später sehen, daß die
Verteilung der Teilchen α für verschiedene Winkel der großen Ablenkung nicht folgen die
Wahrscheinlichkeit Recht zu erwarten, wenn so große Ablenkung von einer großen Anzahl von kleinen
Abweichungen nach oben vorgenommen werden. Es scheint vernünftig, anzunehmen, dass die
Ablenkung durch einen großen Winkel zu einer einzelnen atomaren Begegnung zurückzuführen ist, für
die Chance auf eine zweite Begegnung der Art, dass eine große Ablenkung produzieren, müssen in den
meisten Fällen sehr gering sein. Eine einfache Rechnung zeigt, dass das Atom muss ein Sitz eines
starken elektrischen Feldes, um eine so große Ablenkung in einer einzigen Begegnung zu produzieren.

Kürzlich JJ Thomson **** hat einen Theorie

* Mitgeteilt durch den Autor. Ein kurzer Bericht über dieses Papier wurde auf der Manchester Literary
and Philosophical Society im Februar mitgeteilt, 1911.
** Proc. Roy. Soc. LXXXII, S. 495 (1909)
*** Proc. Roy. Soc. LXXXIII, S. 492 (1910)
**** Camb. Lit. & Phil Soc. xv pt. 5 (1910)

670

erklären, die Streuung von geladenen Teilchen beim Durchgang durch geringen Dicken der Materie.
Das Atom soll der eine Anzahl N von negativ geladenen Blutkörperchen, begleitet von einer gleichen
Menge von positiver Elektrizität aus gleichmäßig über eine Kugel verteilt. Die Ablenkung eines negativ
geladenen Teilchen beim Durchgang durch das Atom ist auf zwei Ursachen zurückzuführen - (1) die
Abstoßung der Blutkörperchen durch das Atom verteilt, und (2) die Anziehungskraft der positiven
Elektrizität im Atom. Die Ablenkung der Teilchen beim Durchgang durch das Atom soll klein sein,
während die durchschnittliche Ablenkung, nachdem eine große Zahl m der Begegnung als übernahm
[die Quadratwurzel] m · θ, wenn θ ist der durchschnittliche Ablenkung durch einen einzigen Atom. Es
konnte gezeigt werden, dass die Anzahl N der Elektronen im Atom aus der Beobachtung der Streuung
ableiten konnte, war experimentell untersucht Crowther * in einer späteren Arbeit werden. Seine
Ergebnisse offenbar bestätigt, der die wichtigsten Schlussfolgerungen der Theorie, und er leitete, auf
der Annahme, daß die positive Elektrizität Zeitpunkt unterbrochen war, dass die Zahl der Elektronen in
einem Atom etwa dreimal sein Atomgewicht wurde.

Die Theorie von JJ Thomson ist auf der Annahme, dass die Streuung durch eine einzige atomare
Begegnung ist klein, und die besondere Struktur für das Atom nicht für eine sehr große Ablenkung der
Durchmesser der Kugel von positiver Elektrizität zugeben, ist winzig im Vergleich mit dem
Durchmesser des Einflussbereichs des Atoms.

Da die α-und β Teilchen durchqueren das Atom, sollte es möglich sein, von einer engen Studie über die
Art der Ablenkung, um eine Vorstellung von der Konstitution des Atoms, die Effekte zu produzieren
Form beobachtet. In der Tat, die Streuung von High-Speed-geladene Teilchen durch die Atome der
Materie ist eine der vielversprechendsten Methoden des Angriffs dieses Problems. Die Entwicklung der
Szintillationsmethode zählen einzigen α Teilchen bietet außergewöhnliche Vorteile der Untersuchung,
und die Untersuchungen von H. Geiger mit dieser Methode haben schon viel zu unserem Wissen über
die Streuung von α-Strahlen von der Materie hat.

§ 2. Wir werden zunächst theoretisch untersucht die einzelnen Begegnungen ** mit einem Atom von
einfacher Struktur, die in der Lage ist,

* Crowther, Proc. Roy. Soc. LXXXIV. S. 226 (1910)


** Die Abweichung eines Teilchens in einem beträchtlichen Winkel von einer Begegnung mit einem
einzigen Atom wird in diesem Papier die Bezeichnung "Single"-Streuung. Die Abweichung eines
Teilchens, die sich aus einer Vielzahl von kleinen Abweichungen wird man als "Verbindung" Streuung.

671

produzieren große Verformungen eines α Teilchen, und vergleichen Sie dann die Folgerungen aus der
Theorie mit den experimentellen Daten zur Verfügung.

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Harold C. Urey (1893-1981), F. G. Brickwedde (1903-1989), & G.
M. Murphy (1903-1968)
A Hydrogen Isotope of Mass 2
Physical Review 39, 164-165 (1932).
Copyright 1932 by the American Physical Society; reproduced with permission.
The proton-electron plot of known atomic nuclei shows some rather marked regularities among atoms
of lower atomic number.[1] Up to O16 a simple step-wise figure appears into which the nuclear species
H2, H3 and He4 could be fitted very nicely. Birge and Menzel[2] have shown that the discrepancy
between the chemical atomic weight of hydrogen and Aston's value by the mass spectrograph could be
accounted for by the assumption of a hydrogen isotope of mass 2 present to the extent of 1 part in 4500
parts of hydrogen of mass 1.
It is possible to calculate with confidence the vapor pressures of the pure substances H1H1, H1H2,
H1H3, in equilibrium with the pure solid phases. It is only necessary to assume that in the Debye theory
of the solid state, θ is inversely proportional to the square root of the masses of these molecules and
that the rotational and vibrational energies of the molecules do not change in the process of
vaporization. These assumptions are in accord with well-established experimental evidence. We find
that the vapor pressures for these molecules in equilibrium with their solids should be in the ratio of
p11:p12:p13 = 1:0.37:0.29. The theory of the liquid state is not so vell understood but it seems
reasonable to believe that the differences in vapor pressure of these molecules in equilibrium with their
liquids whould be rather large and should make possible a rapid concentration of the heavier isotopes,
if they exist, in the residue from the simple evaporation of liquid hydrogen near its triple point.
Accordingly two samples of hydrogen were prepared by evaporating large quantities of liquid
hydrogen and collecting the gas which evaporated from the last fraction of the last cubic centimeter.
The first sample was collected from the end portion of six liters of liquid evaporated at atmospheric
pressure, and the second sample from four liters evaporated at a pressure only a few millimeters above
the triple point. The process of liquefaction has probably no effect in changing the concentration of the
isotopes since no appreciable change was observed in the sample evaporated at atmospheric pressure.
These samples were investigated for the atomic spectra of H2 and H3 in a hydrogen discharge tube run
in Wood's so-called "black stage" by using the second order of a 21 foot grating with a dispersion of
1.31 Å per mm. With the sample evaporated at the boiling point no concentration so high as had been
estimated was detected. We then increased the exposures so that the ratio of the time of exposure to the
minimum required to get the H1 lines on our plates was about 4500:1. Under these conditions we found
in this sample as well as in ordinary hydrogen faint lines at the calculated positions for the lines of H2
accompanying Hβ, Hγ, Hδ. These lines do not agree in wavelength with any molecular lines reported in
the literature.[3] However they were so weak that it was difficult to be sure that they were not ghosts of
the strongly overexposed atomic lines.
The sample of hydrogen evaporated near the triple point shows these lines greatly enhanced, relative to
the lines of H1, over both those of ordinary hydrogen and of the first sample. The relative intensities
can be judged by the number and intensity of the symmetrical ghosts on the plates. The wave-lengths of
the H2 lines appearing on these plates could be easily measured within about 0.02 Å. The following
table gives the mean of the observed displacements of these lines from those of H1 and the calculated
displacements:
Line Hα Hβ Hγ Hδ
Δλ calc. 1.793 1.326 1.185 1.119
Δλ obs.
Ordinary hydrogen -- 1.346 1.206 1.145
1st sample -- 1.330 1.119 1.103
2nd sample 1.820 1.315 1.176 --
2
The H lines are broad, as is to be expected for close unresolved doublets, but they are not as broad and
diffuse as the H1 lines probably due to the smaller Döppler broadening. Although their intensities
relative to the ghosts of the respective H1 lines appear nearly constant for any one sample of hydrogen,
they are not ghosts for their intensities relative to the known ghosts for their intensities are not the same
in the case of ordinary hydrogen and of the 1st sample as they are in the case of the second sample.
They are not molecular lines for they do not appear on a plate taken with the discharge tube in the
"white stage" with the molecular spectrum enhanced (H2γ was found as a slight irregularity on a
microphotometer curve of this plate). Finally the H2α line is resolved into a doublet with a separation of
about 0.16 Å in agreement with the observed separation of the H1α line.
The relative abundance in ordinary hydrogen, judging from relative minimum exposure time is about
1:4000, or less, in agreement with Birge and Menzel's estimate. A similar estimate of the abundance in
the second sample indicated a concentration of about 1 in 800. Thus an appreciable fractionation has
been secured as expected from theory.[4] No evidence for H3 has been secured, but its lines would fall
on regions of our plates where the halation is bad.
The distillation was carried out at the Bureau of Standards by one of us (F.G.B.), who is continuing the
fractionation to secure more highly concentrated samples. The spectroscopic work was done at
Columbia University by the other two (H.C.U. and G.M.M.) who are working on the molecular
spectrum.
Harold C. Urey
F. G. Brickwedde
G. M. Murphy

Columbia University,
New York, N. Y.
Bureau of Standards,
Washington, D. C.
December 5, 1931.

[1]Urey, J. Am. Chem. Soc. 53, 2872 (1931); Johnston, ibid., 53, 2866 (1931).
[2]Birge and Menzel, Phys. Rev. 37, 1669 (1931).
[3]Gale, Monk and Lee, Astrophys. J. 57, 89 (1928); Finkelnburg, Z. Physik 52, 57 (1928); Connelly,
Proc. Phys. Soc. 42, 28 (1929).
[4]Keesom and van Dijk, Proc. Acad. Sci. Amsterdam 34, 52 (1931).

Back to the list of selected historical papers.


Back to the top of Classic Chemistry.
Frederick Soddy (1877-1956)
Intra-atomic Charge.
Nature 92, 399-400 (December 4, 1913)
That the intra-atomic charge of an element is determined by its place in the periodic table rather than by
its atomic weight, as concluded by A. van der Broek (NATURE, November 27, p. 372), is strongly
supported by the recent generalisation as to the radio-elements and the periodic law. The successive
expulsion of one α and two β particles in three radio-active changes in any order brings the intra-atomic
charge of the element back to its initial value, and the element back to its original place in the table,
though its atomic mass is reduced by four units. We have recently obtained something like a direct
proof of van der Broek's view that the intra-atomic charge of the nucleus of an atom is not a purely
positive charge, as on Rutherford's tentative theory. but is the difference between a positive and a
smaller negative charge.

Fajans, in his paper on the periodic law generalisation (Physikal. Zeitsch., 1913, vol. xiv., p. 131),
directed attention to the fact that the changes of chemical nature consequent upon the expulsion of α
and β particles are precisely of the same kind as in ordinary electrochemical changes of valency. He
drew from this the conclusion that radio-active changes must occur in the same region of atomic
structure as ordinary chemical changes, rather than with a distinct inner region of structure or
"nucleus," as hitherto supposed. In my paper on the same generalisation, published immediately after
that of Fajans (Chem. News, February 28), I laid stress on the absolute identity of chemical properties
of different elements occupying the same place in the periodic table.

A simple deduction from this view supplied me with a means of testing the correctness of Fajans's
conclusion that radio-changes and chemical changes are concerned with the same region of atomic
structure. On my view his conclusion would involve nothing else than that, for example, uranium in its
tetravalent uranous compounds must be chemically identical with and non-separable from thorium
compounds. For uranium X, formed from uranium I by expulsion of an α particle, is chemically
identical with thorium, as also is ionium formed in the same way from uranium II. Uranium X loses
two β particles and passes back into uranium II, chemically identical with uranium. Uranous salts also
lose two electrons and pass into the more hexavalent uranyl compounds. If these electrons come from
the same region of the atom uranous salts should be chemically non-separable from thorium salts. But
they are not.

There is a strong resemblance in chemical character between uranous and thorium salts, and I asked
Mr. Fleck to examine whether they could be separated by chemical methods when mixed, the uranium
being kept unchanged throughout in the uranous or tetravalent condition. Mr. Fleck will publish the
experiments separately, and I am indebted to him for the result that the two classes of compounds can
readily be separated by fractionation methods.

This, I think, amounts to a proof that the electrons expelled as β rays come from a nucleus not capable
of supplying electrons to or withdrawing them from the ring, though this ring is capable of gaining or
losing electrons from the exterior during ordinary electrochemical changes of valency.
I regard van der Broek's view, that the number representing the net positive charge of the nucleus is the
number of the place which the element occupies in the periodic table when all the possible places from
hydrogen to uranium are arranged in sequence, as practically proved so far as the relative value of the
charge for the members of the end of the sequence, from thallium to uranium, is concerned. We are left
uncertain as to the absolute value of the charge, because of the doubt regarding the exact number of
rare-earth elements that exist. If we assume that all of these are known, the value for the positive charge
of the nucleus of the uranium atom is about 90. Whereas if we make the more doubtful assumption that
the periodic table runs regularly, as regards numbers of places, through the rare-earth group, and that
between barium and radium, for example, two complete long periods exist, the number is 96. In either
case it is appreciably less than 120, the number were the charge equal to one-half the atomic weight, as
it would be if the nucleus were made out of α particles only. Six nuclear electrons are known to exist in
the uranium atom, which expels in its changes six β rays. Were the nucleus made up of α particles there
must be thirty or twenty-four respectively nuclear electrons, compared with ninety-six or 102
respectively in the ring. If, as has been suggested, hydrogen is a second component of atomic structure,
there must be more than this. But there can be no doubt that there must be some, and that the central
charge of the atom on Rutherford's theory cannot be a pure positive charge, but must contain electrons,
as van der Broek concludes.

So far as I personally am concerned, this has resulted in a great clarification of my ideas, and it may be
helpful to others, though no doubt there is little originality in it. The same algebraic sum of the positive
and negative charges in the nucleus, when the arithmetical sum is different, gives what I call "isotopes"
or "isotopic elements," because they occupy the same place in the periodic table. They are chemically
identical, and save only as regards the relatively few physical properties which depend on atomic mass
directly, physically identical also. Unit changes of this nuclear charge, so reckoned algebraically, give
the successive places in the periodic table. For any one "place," or any one nuclear charge, more than
one number of electrons in the outer-ring system may exist, and in such a case the element exhibits
variable valency. But such changes of number, or of valency, concern only the ring and its external
environment. There is no in- and out-going of electrons between ring and nucleus.

FREDERICK SODDY
Physical Chemistry Laboratory,
University of Glasgow.

--------------------------------------------------------------------------------
Back to the list of selected historical papers.
Back to the top of Classic Chemistry.The Scattering of α and β Particles by Matter and the Structure of
the Atom
E. Rutherford, F.R.S.*
Philosophical Magazine
Series 6, vol. 21
May 1911, p. 669-688

--------------------------------------------------------------------------------

669

§ 1. It is well known that the α and the β particles suffer deflexions from their rectilinear paths by
encounters with atoms of matter. This scattering is far more marked for the β than for the α particle on
account of the much smaller momentum and energy of the former particle. There seems to be no doubt
that such swiftly moving particles pass through the atoms in their path, and that the deflexions observed
are due to the strong electric field traversed within the atomic system. It has generally been supposed
that the scattering of a pencil of α or β rays in passing through a thin plate of matter is the result of a
multitude of small scatterings by the atoms of matter traversed. The observations, however, of Geiger
and Marsden** on the scattering of α rays indicate that some of the α particles, about 1 in 20,000 were
turned through an average angle of 90 degrees in passing though a layer of gold-foil about 0.00004 cm.
thick, which was equivalent in stopping-power of the α particle to 1.6 millimetres of air. Geiger***
showed later that the most probable angle of deflexion for a pencil of α particles being deflected
through 90 degrees is vanishingly small. In addition, it will be seen later that the distribution of the α
particles for various angles of large deflexion does not follow the probability law to be expected if such
large deflexion are made up of a large number of small deviations. It seems reasonable to suppose that
the deflexion through a large angle is due to a single atomic encounter, for the chance of a second
encounter of a kind to produce a large deflexion must in most cases be exceedingly small. A simple
calculation shows that the atom must be a seat of an intense electric field in order to produce such a
large deflexion at a single encounter.

Recently Sir J. J. Thomson**** has put forward a theory to

* Communicated by the Author. A brief account of this paper was communicated to the Manchester
Literary and Philosophical Society in February, 1911.
** Proc. Roy. Soc. lxxxii, p. 495 (1909)
*** Proc. Roy. Soc. lxxxiii, p. 492 (1910)
**** Camb. Lit. & Phil Soc. xv pt. 5 (1910)

670

explain the scattering of electrified particles in passing through small thicknesses of matter. The atom is
supposed to consist of a number N of negatively charged corpuscles, accompanied by an equal quantity
of positive electricity uniformly distributed throughout a sphere. The deflexion of a negatively
electrified particle in passing through the atom is ascribed to two causes -- (1) the repulsion of the
corpuscles distributed through the atom, and (2) the attraction of the positive electricity in the atom.
The deflexion of the particle in passing through the atom is supposed to be small, while the average
deflexion after a large number m of encounters was taken as [the square root of] m · θ, where θ is the
average deflexion due to a single atom. It was shown that the number N of the electrons within the
atom could be deduced from observations of the scattering was examined experimentally by Crowther*
in a later paper. His results apparently confirmed the main conclusions of the theory, and he deduced,
on the assumption that the positive electricity was continuous, that the number of electrons in an atom
was about three times its atomic weight.

The theory of Sir J. J. Thomson is based on the assumption that the scattering due to a single atomic
encounter is small, and the particular structure assumed for the atom does not admit of a very large
deflexion of diameter of the sphere of positive electricity is minute compared with the diameter of the
sphere of influence of the atom.

Since the α and β particles traverse the atom, it should be possible from a close study of the nature of
the deflexion to form some idea of the constitution of the atom to produce the effects observed. In fact,
the scattering of high-speed charged particles by the atoms of matter is one of the most promising
methods of attack of this problem. The development of the scintillation method of counting single α
particles affords unusual advantages of investigation, and the researches of H. Geiger by this method
have already added much to our knowledge of the scattering of α rays by matter.

§ 2. We shall first examine theoretically the single encounters** with an atom of simple structure,
which is able to

* Crowther, Proc. Roy. Soc. lxxxiv. p. 226 (1910)


** The deviation of a particle throughout a considerable angle from an encounter with a single atom
will in this paper be called 'single' scattering. The deviation of a particle resulting from a multitude of
small deviations will be termed 'compound' scattering.

671

produce large deflections of an α particle, and then compare the deductions from the theory with the
experimental data available.

Consider an atom which contains a charge ±Ne at its centre surrounded by a sphere of electrification
containing a charge ±Ne [N.B. in the original publication, the second plus/minus sign is inverted to be a
minus/plus sign] supposed uniformly distributed throughout a sphere of radius R. e is the fundamental
unit of charge, which in this paper is taken as 4.65 x 10¯10 E.S. unit. We shall suppose that for
distances less than 10¯12 cm. the central charge and also the charge on the alpha particle may be
supposed to be concentrated at a point. It will be shown that the main deductions from the theory are
independent of whether the central charge is supposed to be positive or negative. For convenience, the
sign will be assumed to be positive. The question of the stability of the atom proposed need not be
considered at this stage, for this will obviously depend upon the minute structure of the atom, and on
the motion of the constituent charged parts.

In order to form some idea of the forces required to deflect an alpha particle through a large angle,
consider an atom containing a positive charge Ne at its centre, and surrounded by a distribution of
negative electricity Ne uniformly distributed within a sphere of radius R. The electric force X and the
potential V at a distance r from the centre of an atom for a point inside the atom, are given by

Suppose an α particle of mass m and velocity u and charge E shot directly towards the centre of the
atom. It will be brought to rest at a distance b from the centre given by

It will be seen that b is an important quantity in later calculations. Assuming that the central charge is
100 e, it can be calculated that the value of b for an α particle of velocity 2.09 x 109 cms. per second is
about 3.4 x 10¯12 cm. In this calculation b is supposed to be very small compared with R. Since R is
supposed to be of the order of the radius of the atom, viz. 10¯8 cm., it is obvious that the α particle
before being turned back penetrates so close to

672

the central charge, that the field due to the uniform distribution of negative electricity may be
neglected. In general, a simple calculation shows that for all deflexions greater than a degree, we may
without sensible error suppose the deflexion due to the field of the central charge alone. Possible single
deviations due to the negative electricity, if distributed in the form of corpuscles, are not taken into
account at this stage of the theory. It will be shown later that its effect is in general small compared
with that due to the central field.

Consider the passage of a positive electrified particle close to the centre of an atom. Supposing that the
velocity of the particle is not appreciably changed by its passage through the atom, the path of the
particle under the influence of a repulsive force varying inversely as the square of the distance will be
an hyperbola with the centre of the atom S as the external focus. Suppose the particle to enter the atom
in the direction PO (fig. 1), and that the direction of motion

on escaping the atom is OP'. OP and OP' make equal angles with the line SA, where A is the apse of the
hyperbola. p = SN = perpendicular distance from centre on direction of initial motion of particle.
673

Let angle POA = θ.

Let V = velocity of particle on entering the atom, ν its velocity at A, then from consideration of angular
momentum

pV = SA . ν.

From conservation of energy

(1/2)mV2 = (1/2)mν2 - (NeE / SA),

ν2 = V2 (1 - (b / SA)).

Since the eccentricity is sec θ,

SA = SO + OA = p cosec θ(1 + cos θ)

= p cot θ / 2

p2 = SA(SA - b) = p cot θ/2(p cot θ/2 - b),

therefore b = 2p cot θ.

The angle of deviation θ of the particles is π - 2θ and

cot θ / 2 = (2p / b) * . . . . (1)

This gives the angle of deviation of the particle in terms of b, and the perpendicular distance of the
direction of projection from the centre of the atom.

For illustration, the angle of deviation f for different values of p / b are shown in the following table: --

p / b . . . . . 10 5 2 1 0.5 0.25 0.125


f . . . . . . . 5°.7 11°.4 28° 53° 90° 127° 152°

§ 3. Probability of single deflexion through any angle

Suppose a pencil of electrified particles to fall normally on a thin screen of matter of thickness t. With
the exception of the few particles which are scattered through a large angle, the particles are supposed
to pass nearly normally through the plate with only a small change of velocity. Let n = number of atoms
in unit volume of material. Then the number of collisions of the particle with the atom of radius R is
πR2nt in the thickness t.

* A simple consideration shows that the deflexion is unaltered if the forces are attractive instead of
repulsive.

674

The probability m of entering an atom within a distance p of its center is given by

m = πp2nt.

Chance dm of striking within radii p and p + dp is given by

dm = 2πpnt . dp = (π / 4)ntb2 cot f/2 cosec2 f/2 df . . . . (2)

since

cot f/2 = 2p / b

The value of dm gives the fraction of the total number of particles which are deviated between the
angles f and f + df.

The fraction p of the total number of particles which are deflected through an angle greater than f is
given by

p = (π / 4)ntb2 cot2 f/2 . . . . . . (3)

The fraction p which is deflected between the angles f1 and f2 is given by


p = (π / 4)ntb2 (cot2 f1/2 - cot2 f2/2) . . . . . . . . . . . . . (4)

It is convenient to express the equation (2) in another form for comparison with experiment. In the case
of the α rays, the number of scintillations appearing on the constant area of the zinc sulphide screen are
counted for different angles with the direction of incidence of the particles. Let r = distance from point
of incidence of α rays on scattering material, then if Q be the total number of particles falling on the
scattering material, the number y of α particles falling on unit area which are deflected through an
angle f is given by

y = Qdm / 2πr2 sin f . df = (ntb2 . Q . cosec4 f/2) / 16r2 . . . . . . . (5)

Since b = 2NeE / mu2, we see from this equation that the number of α particles (scintillations) per unit
area of zinc sulphide screen at a given distance r from the point of

675

Incidence of the rays is proportional to

(1) cosec4 f/2 or 1/f4 if f be small;


(2) thickness of scattering material t provided this is small;
(3) magnitude of central charge Ne;
(4) and is inversely proportional to (mu2)2, or to the fourth power of the velocity if m be constant.
In these calculations, it is assumed that the α particles scattered through a large angle suffer only one
large deflexion. For this to hold, it is essential that the thickness of the scattering material should be so
small that the chance of a second encounter involving another large deflexion is very small. If, for
example, the probability of a single deflexion f in passing through a thickness t is 1/1000, the
probability of two successive deflexions each of value f is 1/106 , and is negligibly small.

The angular distribution of the α particles scattered from a thin metal sheet affords one of the simplest
methods of testing the general correctness of this theory of single scattering. This has been done
recently for α rays by Dr. Geiger,* who found that the distribution for particles deflected between 30°
and 150° from a thin gold-foil was in substantial agreement with the theory. A more detailed account of
these and other experiments to test the validity of the theory will be published later.

§ 4. Alteration of velocity in an atomic encounter

It has so far been assumed that an α or β particle does not suffer an appreciable change of velocity as
the result of a single atomic encounter resulting in a large deflexion of the particle. The effect of such
an encounter in altering the velocity of the particle can be calculated on certain assumptions. It is
supposed that only two systems are involved, viz., the swiftly moving particle and the atom which it
traverses supposed initially at rest. It is supposed that the principle of conservation of momentum and
of energy applies, and that there is no appreciable loss of energy or momentum by radiation.

* Manch. Lit. & Phil. Soc. 1910.

676

Let m be mass of the particle,

ν1 = velocity of approach,
ν2 = velocity of recession,
M= mass of atom,
V = velocity communicated to atom as result of encounter.
Let OA (fig. 2) represent in magnitude and direction the momentum mν1 of the entering particle, and
OB the momentum of the receding particle which has been turned through an angle AOB = f. Then BA
represents in magnitude and direction the momentum MV of the recoiling atom.

(MV)2 = (mν1)2 + (mν2)2 - 2m2ν1ν2 cos f . . . (1)

By conservation of energy

MV2 = mν12 - mν22 . . . . .(2)

Suppose M/m = K and ν2 = pν1, where p < 1.


From (1) and (2),

Consider the case of an α particle of atomic weight 4, deflected through an angle of 90° by an
encounter with an atom of gold of atomic weight 197.

Since K= 49 nearly,
or the velocity of the particle is reduced only about 2 per cent. by the encounter.

In the case of aluminium K=27/4 and for f = 90° p = 0.86.

It is seen that the reduction of velocity of the α particle becomes marked on this theory for encounters
with the lighter atoms. Since the range of an α particle in air or other matter is approximately
proportional to the cube of the velocity, it follows that an α particle of range 7 cms. has its range
reduced to 4.5 cms. after incurring a single

677

deviation of 90° in traversing an aluminium atom. This is of a magnitude to be easily detected


experimentally. Since the value of K is very large for an encounter of a β particle with an atom, the
reduction of velocity on this formula is very small.

Some very interesting cases of the theory arise in considering the changes of velocity and the
distribution of scattered particles when the α particle encounters a light atom, for example a hydrogen
or helium atom. A discussion of these and similar cases is reserved until the question has been
examined experimentally.

§ 5. Comparison of single and compound scattering

Before comparing the results of theory with experiment, it is desirable to consider the relative
importance of single and compound scattering in determining the distribution of the scattered particles.
Since the atom is supposed to consist of a central charge surrounded by a uniform distribution of the
opposite sign through a sphere of radius R, the chance of encounters with the atom involving small
deflexions is very great compared with the change of a single large deflexion.

This question of compound scattering has been examined by Sir J. J. Thomson in the paper previously
discussed (§1). In the notation of this paper, the average deflexion f1 due to the field of the sphere of
positive electricity of radius R and quantity Ne was found by him to be

The average deflexion f2 due to the N negative corpuscles supposed distributed uniformly throughout
the sphere was found to be

The mean deflexion due to both positive and negative electricity was taken as

(f12 + f22)1/2
In a similar way, it is not difficult to calculate the average deflexion due to the atom with a central
charge discussed in this paper.

Since the radial electric field X at any distance r from the

678

centre is given by

it is not difficult to show that the deflexion (supposed small) of an electrified particle due to this field is
given by

Where p is the perpendicular from the center on the path of the particles and b has the same value as
before. It is seen that the value of θ increases with diminution of p and becomes great for small value of
f.

Since we have already seen that the deflexions become very large for a particle passing near the center
of the atom, it is obviously not correct to find the average value by assuming θ is small.

Taking R of the order 10-8 cm., the value of p for a large deflexions is for α and β particles of the order
10-11 cm. Since the chance of an encounter involving a large deflexion is small compared with the
chance of small deflexions, a simple consideration shows that the average small deflexion is practically
unaltered if the large deflexions are omitted. This is equivalent to integrating over that part of the cross
section of the atom where the deflexions are small and neglecting the small central area. It can in this
way be simply shown that the average small deflexion is given by

This value of f1 for the atom with a concentrated central charge is three times the magnitude of the
average deflexion for the same value of Ne in the type of atom examined by Sir J. J. Thomson.
Combining the deflexions due to the electric field and to the corpuscles, the average deflexion is
It will be seen later that the value of N is nearly proportional to the atomic weight, and is about 100 for
gold. The effect due to scattering of the individual corpuscles expressed by the second term of the
equation is consequently small for heavy atoms compared with that due to the distributed electric field.

679

Neglecting the second term, the average deflexion per atom is 3πb / 8R. We are now in a position to
consider the relative effects on the distribution of particles due to single and to compound scattering.
Following J. J. Thomson's argument, the average deflexion θ after passing through a thickness t of
matter is proportional to the square root of the number of encounters and is given by

where n as before is equal to the number of atoms per unit volume.

The probability p1 for compound scattering that the deflexion of the particle is greater than f is equal to
e-f2/ θt2.

Consequently

Next suppose that single scattering alone is operative. We have seen (§3) that the probability p2 of a
deflexion greater than f is given by

p = (π / 4)b2 . n . t (cot2 f / 2) .

By comparing these two equations

p2 log p1= - 0.181f2 cot2 f / 2 ,

f is sufficiently small that

tan f/2 = f/2,

p2 log p1= -0.72


If we suppose that

p2 = 0.5, then p1 = 0.24

If

p2 = 0.1, then p1 = 0.0004

It is evident from this comparison, that the probability for any given deflexion is always greater for
single than for compound scattering. The difference is especially marked when only a small fraction of
the particles are scattered through any given angle. It follows from this result that the distribution of
particles due to encounters with the atoms is for small thicknesses mainly governed by single
scattering. No doubt compound scattering produces some effect in equalizing the distribution of the
scattered particles; but its effect becomes relatively smaller, the smaller the fraction of the particles
scattered through a given angle.

680

§6. Comparison of Theory with Experiments

On the present theory, the value of the central charge Ne is an important constant, and it is desirable to
determine its value for different atoms. This can be most simply done by determining the small fraction
of α or β particles of known velocity falling on a thin metal screen, which are scattered between f and f
+ df where f is the angle of deflexion, The influence of compound scattering should be small when this
fraction is small.

Experiments in these directions are in progress, but it is desirable at this stage to discuss in the light of
the present theory the data already published on scattering of α and β particles,

The following points will be discussed: --

(a) The 'diffuse reflexion' of α particles, i.e. the scattering of α particles through large angles (Geiger
and Marsden.)
(b) The variation of diffuse reflexion with atomic weight of the radiator (Geiger and Marsden.)
(c) The average scattering of a pencil of α rays transmitted through a thin metal plate (Geiger.)
(d) The experiments of Crowther on the scattering of β rays of different velocities by various metals.
(a) In the paper of Geiger and Marsden (loc.cit.) on the diffuse reflexion of α particles falling on
various substances it was shown that about 1/8000 of the α particles from radium C falling on a thick
plate of platinum are scattered back in the direction of the incidence. This fraction is deduced on the
assumption that the α particles are uniformly scattered in all directions , the observation being made for
a deflexion of about 90°. The form of experiment is not very suited for accurate calculation, but from
the data available it can be shown that the scattering observed is about that to be expected on the theory
if the atom of platinum has a central charge of about 100 e.

In their experiments on this subject, Geiger and Marsden gave the relative number of α particles
diffusely reflected from thick layers of different metals, under similar conditions . The numbers
obtained by them are given in the table below, where z represents the relative number of scattered
particles, measured by the of scintillations per minute on a zinc sulphide screen.

681

Metal Atomic weight z z / A3/2


Lead 207 62 208
Gold 197 67 242
Platinum 195 63 232
Tin 119 34 226
Silver 108 27 241
Copper 64 14.5 225
Iron 56 10.2 250
Aluminium 27 3.4 243
Average 233
On the theory of single scattering, the fraction of the total number of α particles scattered through any
given angle in passing through a thickness t is proportional to n . A2t , assuming that the central charge
is proportional to the atomic weight A. In the present case, the thickness of matter from which the
scattered α particles are able to emerge and affect the zinc sulphide screen depends on the metal. Since
Bragg has shown that the stopping power of an atom for an α particle is proportional to the square root
of its atomic weight, the value of nt for different elements is proportional to 1 / [square root of] A . In
this case t represents the greatest depth from which the scattered α particles emerge. The number z of α
particles scattered back from a thick layer is consequently proportional to A3/2 or z / A3/2 should be a
constant.

To compare this deduction with experiment, the relative values of the latter quotient are given in the
last column . Considering the difficulty of the experiments, the agreement between theory and
experiment is reasonably good.*

The single large scattering of α particles will obviously affect to some extent the shape of the Bragg
ionization curve for a pencil of α rays. This effect of large scattering should be marked when the α rays
have traversed screens of metals of high atomic weight, but should be small for atoms of light atomic
weight.

(c) Geiger made a careful determination of the scattering of α particles passing through thin metal foils,
by the scintillation method, and deduced the most probable angle
* The effect of change of velocity in an atomic encounter is neglected in this calculation.

682

through which the α particles are deflected in passing through known thickness of different kinds of
matter.

A narrow pencil of homogeneous α rays was used as a source. After passing through the scattering foil ,
the total number of α particles are deflected through different angles was directly measured. The angle
for which the number of scattered particles was a maximum was taken as the most probable angle. The
variation of the most probable angle with thickness of matter was determined, but calculation from
these data is somewhat complicated by the variation of velocity of the α particles in their passage
through the scattering material. A consideration of the curve of distribution of the α particles given in
the paper (loc.cit. p. 498) shows that the angle through which half the particles are scattered is about 20
per cent greater than the most probable angle.

We have already seen that compound scattering may become important when about half the particles
are scattered through a given angle, and it is difficult to disentangle in such cases the relative effects
due to the two kinds of scattering. An approximate estimate can be made in the following ways: --
From (§5) the relation between the probabilities p1 and p2 for compound and single scattering
respectively is given by

p2 log p1= -0.721.

The probability q of the combined effects may as a first approximation be taken as

q = (p12 +p22)1/2.
If q = 0.5, it follows that

p1 = 0.2 and p2 = 0.46

We have seen that the probability p2 of a single deflexion greater than f is given by

p2 = (π / 4)n . t . b2 (cot2 f / 2) .

Since in the experiments considered f is comparatively small

Geiger found that the most probable angle of scattering of the α rays in passing through a thickness of
gold equivalent in stopping power to about 0.76 cm. of air was 1° 40'. The angle f through which half
the α particles are tuned thus corresponds to 2° nearly.

t = 0.00017 cm.; n = 6.07 x 1022;

u (average value) = 1.8 x 109.

E/m = 1.5 x 1014 E.S. units; e = 4.65 x 10-10,

683

Taking the probability of single scattering = 0.46 and substituting the above value in the formula, the
value of N for gold comes out to be 97.

For a thickness of gold equivalent in stopping power to 2.12 cms, of air, Geiger found the most
probable angle to be 3° 40'. In this case, t = 0.00047, f = 4°.4, and average u =1.7 x 109, and N comes
out to be 114.

Geiger showed that the most probable angle of deflexion for an atom was nearly proportional to its
atomic weight. It consequently follows that the value for N for different atoms should be nearly
proportional to their atomic weights, at any rate for atomic weights between gold and aluminum.
Since the atomic weight of platinum is nearly equal to that of gold, it follows from these considerations
that the magnitude of the diffuse reflexion of α particles through more than 90° from gold and the
magnitude of the average small angle scattering of a pencil of rays in passing through gold-foil are both
explained on the hypothesis of single scattering by supposing the atom of gold has a central charge of
about 100 e.

(d) Experiments of a Crowther on scattering of α rays. -- We shall now consider how far the
experimental results of Crowther on scattering of β particles of different velocities by various materials
can be explained on the general theory of single scattering. On this theory, the fraction of β particles p
turned through an angel greater than f is given by

p = (π / 4)n . t . b2 (cot2 f / 2) .

In most of Crowther's experiments f is sufficiently small that tan f/2 may be put equal to f/2 without
much error. Consequently

f2 = 2πn . t . b2 if p =1/2

On the theory of compound scattering, we have already seen that the chance p1 that the deflexion of the
particles is greater than f is given by

Since in the experiments of Crowther the thickness t of matter was determined for which p1 = 1/2,

f2 = 0.96π n t b2.

For the probability of 1/2, the theories of single and compound

684

scattering are thus identical in general form, but differ by a numerical constant. It is thus clear that the
main relations on the theory of compound scattering of Sir J. J. Thomson, which were verified
experimentally by Crowther, hold equally well on the theory of single scattering.

For example, it tm be the thickness for which half the particles are scattered through an angle f,
Crowther showed that f / [square root of] tm and also mu2 / E times [square root of] tm were constants
for a given material when f was fixed. These relations hold also on the theory of single scattering.
Notwithstanding this apparent similarity in form, the two theories are fundamentally different. In one
case, the effects observed are due to cumulative effects of small deflexion, while in the other the large
deflexions are supposed to result from a single encounter. The distribution of scattered particles is
entirely different on the two theories when the probability of deflexion greater than f is small.

We have already seen that the distribution of scattered α particles at various angles has been found by
Geiger to be in substantial agreement with the theory of single scattering, but can not be explained on
the theory of compound scattering alone. Since there is every reason to believe that the laws of
scattering of α and β particles are very similar, the law of distribution of scattered β particles should be
the same as for α particles for small thicknesses of matter. Since the value of mu2 / E for β particles is
in most cases much smaller than the corresponding value for the α particles, the chance of large single
deflexions for β particles in passing through a given thickness of matter is much greater than for α
particles. Since on the theory of single scattering the fraction of the number of particles which are
undeflected through this angle is proportional to kt, where t is the thickness supposed small and k a
constant, the number of particles which are undeflected through this angle is proportional to 1 - kt.
From considerations based on the theory of compound scattering, Sir J.J. Thomson deduced that the
probability of deflexion less than f is proportional to 1 - em / t where m is a constant for any given
value of f.

The correctness of this latter formula was tested by Crowther by measuring electrically the fraction I /
Io of the scattered β particles which passed through a circular opening subtending an angle of 36° with
the scattering material. If

I / Io = 1 - 1 - em / t,

the value of I should decrease very slowly at first with

685

increase of t. Crowther, using aluminium as scattering material, states that the variation of I / Io was in
good accord with this theory for small values of t. On the other hand, if single scattering be present, as
it undoubtedly is for α rays, the curve showing the relation between I / Io and t should be nearly linear
in the initial stages. The experiments of Marsden* on scattering of β rays, although not made with quite
so small a thickness of aluminium as that used by Crowther, certainly support such a conclusion.
Considering the importance of the point at issue, further experiments on this question are desirable.

From the table given by Crowther of the value f / [square root of] tm for different elements for β rays of
velocity 2.68 x 10-10 cms. per second, the value of the central charge Ne can be calculated on the
theory of single scattering. It is supposed, as in the case of the α rays, that for given value of f / [square
root of] tm the fraction of the β particles deflected by single scattering through an angle greater than f is
0.46 instead of 0.5
The value of N calculated from Crowther's data are given below.

Element Atomic weight f / [square root of] tm N


Aluminium 27 4.25 22
Copper 63.2 10.0 42
Silver 108 29 138
Platnium 194 29 138

It will be remembered that the values of N for gold deduced from scattering of the α rays were in two
calculations 97 and 114. These numbers are somewhat smaller than the values given above for platinum
(viz. 138), whose atomic weight is not very different from gold. Taking into account the uncertainties
involved in the calculation from the experimental data, the agreement is sufficiently close to indicate
that the same general laws of scattering hold for the α and β particles, notwithstanding the wide
differences in the relative velocity and mass of these particles.

As in case of the α rays, the value of N should be most simply determined for any given element by
measuring

* Phil. Mag. xviii. p. 909 (1909)

686

the small fraction of the incident β particles scattered through a large angle. In this way, possible errors
due to small scattering will be avoided.

The scattering data for the β rays, as well as for the α rays indicate that the central charge in an atom is
approximately proportional to its atomic weight. This falls in with the experimental deductions of
Schmidt.* In his theory of absorption of β rays, he supposed that in traversing a thin sheet of matter, a
small fraction α of the particles are stopped, and a small fraction β are reflected or scattered back in the
direction of incidence. From comparison of the absorption curves of different elements, he deduced that
the value of the constant β for different elements is proportional to nA2 where n is the number of atoms
per unit volume and A the atomic weight of the element. This is exactly the relation to be expected on
the theory of single scattering if the central charge on an atom is proportional to its atomic weight.

§7. General Considerations

In comparing the theory outlined in this paper with the experimental results, it has been supposed that
the atom consists of a central charge supposed concentrated at a point, and that the large single
deflexions of the α and β particles are mainly due to their passage through the strong central field. The
effect of the equal and opposite compensation charge supposed distributed uniformly throughout a
sphere has been neglected. Some of the evidence in support of these assumptions will now be briefly
considered. For concreteness, consider the passage of a high speed α particle through an atom having a
positive central charge Ne, and surrounded by a compensating charge of N electrons. Remembering
that the mass, momentum, and kinetic energy of the α particle are very large compared with the
corresponding values of an electron in rapid motion, it does not seem possible from dynamic
considerations that an α particle can be deflected through a large angle by a close approach to an
electron, even if the latter be in rapid motion and constrained by strong electrical forces. It seems
reasonable to suppose that the chance of single deflexions through a large angle due to this cause, if not
zero, must be exceedingly small compared with that due to the central charge.

It is of interest to examine how far the experimental evidence throws light on the question of extent of
the

Annal. d. Phys. iv. 23. p. 671 (1907)

687

distribution of central charge. Suppose, for example, the central charge to be composed of N unit
charges distributed over such a volume that the large single deflexions are mainly due to the constituent
charges and not to the external field produced by the distribution. It has been shown (§3) that the
fraction of the α particles scattered through a large angle is proportional to (NeE)2, where Ne is the
central charge concentrated at a point and E the charge on the deflected particles, If, however, this
charge is distributed in single units, the fraction of the α particles scattered through a given angle is
proportional of Ne2 instead of N2e2. In this calculation, the influence of mass of the constituent
particle has been neglected, and account has only been taken of its electric field. Since it has been
shown that the value of the central point charge for gold must be about 100, the value of the distributed
charge required to produce the same proportion of single deflexions through a large angle should be at
least 10,000. Under these conditions the mass of the constituent particle would be small compared with
that of the α particle, and the difficulty arises of the production of large single deflexions at all. In
addition, with such a large distributed charge, the effect of compound scattering is relatively more
important than that of single scattering. For example, the probable small angle of deflexion of pencil of
α particles passing through a thin gold foil would be much greater than that experimentally observed by
Geiger (§ b-c). The large and small angle scattering could not then be explained by the assumption of a
central charge of the same value. Considering the evidence as a whole, it seems simplest to suppose
that the atom contains a central charge distributed through a very small volume, and that the large
single deflexions are due to the central charge as a whole, and not to its constituents. At the same time,
the experimental evidence is not precise enough to negative the possibility that a small fraction of the
positive charge may be carried by satellites extending some distance from the centre. Evidence on this
point could be obtained by examining whether the same central charge is required to explain the large
single deflexions of α and β particles; for the α particle must approach much closer to the center of the
atom than the β particle of average speed to suffer the same large deflexion.

The general data available indicate that the value of this central charge for different atoms is
approximately proportional to their atomic weights, at any rate of atoms heavier than aluminium. It will
be of great interest to examine

688

experimentally whether such a simple relation holds also for the lighter atoms. In cases where the mass
of the deflecting atom (for example, hydrogen, helium, lithium) is not very different from that of the α
particle, the general theory of single scattering will require modification, for it is necessary to take into
account the movements of the atom itself (see § 4).

It is of interest to note that Nagaoka* has mathematically considered the properties of the Saturnian
atom which he supposed to consist of a central attracting mass surrounded by rings of rotating
electrons. He showed that such a system was stable if the attracting force was large. From the point of
view considered in his paper, the chance of large deflexion would practically be unaltered, whether the
atom is considered to be disk or a sphere. It may be remarked that the approximate value found for the
central charge of the atom of gold (100 e) is about that to be expected if the atom of gold consisted of
49 atoms of helium, each carrying a charge of 2 e. This may be only a coincidence, but it is certainly
suggestive in view of the expulsion of helium atoms carrying two unit charges from radioactive matter.

The deductions from the theory so far considered are independent of the sign of the central charge, and
it has not so far been found possible to obtain definite evidence to determine whether it be positive or
negative. It may be possible to settle the question of sign by consideration of the difference of the laws
of absorption of the β particles to be expected on the two hypothesis, for the effect of radiation in
reducing the velocity of the β particle should be far more marked with a positive than with a negative
center. If the central charge be positive, it is easily seen that a positively charged mass if released from
the center of a heavy atom, would acquire a great velocity in moving through the electric field. It may
be possible in this way to account for the high velocity of expulsion of α particles without supposing
that they are initially in rapid motion within the atom.

Further consideration of the application of this theory to these and other questions will be reserved for a
later paper, when the main deductions of the theory have been tested experimentally. Experiments in
this direction are already in progress by Geiger and Marsden.

University of Manchester
April 1911

Nagaoka, Phil. Mag. vii. p. 445 (1904). Pierre Curie (1859-1906) and Marie Sklodowska Curie (1867-
1934)
On a New Radioactive Substance Contained in Pitchblende[1]
note by M. P. Curie and Mme. S. Curie, presented by M. Becquerel
Comptes Rendus 127, 175-8 (1898) translated and reprinted in Henry A. Boorse and Lloyd Motz, eds.,
The World of the Atom, Vol. 1 (New York: Basic Books, 1966)

Certain minerals containing uranium and thorium (pitchblende, chalcolite, uranite) are very active from
the point of view of the emission of Becquerel rays. In a previous paper, one of us has shown that their
activity is even greater than that of uranium and thorium, and has expressed the opinion that this effect
was attributable to some other very active substance included in small amounts in these minerals.[2]

The study of uranium and thorium compounds has shown in fact that the property of emitting rays
which make the air conducting and which affect photographic plates, is a specific property of uranium
and thorium that occurs in all compounds of these metals, being weaker in proportion as the active
metal in the compound is diminished. The physical state of the substances appears to have an entirely
secondary importance. Various experiments have shown that the state of mixture of these substances
seems to act only to vary the proportions of the active bodies and the absorption produced by the inert
substances. Certain causes (such as the presence of impurities) which have so great an effect on the
phosphorescence or fluorescence are here entirely without effect. It is therefore very probable that if
certain minerals are more active than uranium and thorium, it is because they contain a substance more
active than these metals.

We have sought to isolate this substance in pitchblende and experiment has just confirmed the
preceding conjectures.

Our chemical researches have been guided constantly by a check of the radiant activity of the separated
products in each operation. Each product was placed on one of the plates of a condenser and the
conductivity acquired by the air was measured with the aid of an electrometer and a piezoelectric
quartz, as in the work cited above. One has thus not only an indication but a number which gives a
measure of the strength of the product in the active substance.

The pitchblende which we have analysed was approximately two and a half times more active than
uranium in our plate apparatus. We have treated it with acids and have treated the solutions obtained
with hydrogen sulfide. Uranium and thorium remain in solution. We have verified the following facts:

The precipitated sulphides contain a very active substance together with lead, bismuth, copper, arsenic,
and antimony. This substance is completely insoluble in the ammonium sulphide which separates it
from arsenic and antimony. The sulphides insoluble in ammonium sulphide being dissolved in nitric
acid, the active substance may be partially separated from lead by sulphuric acid. On washing lead
sulfate with dilute sulphuric acid, most of the active substance entrained with the lead sulphate is
dissolved.

The active substance present in solution with bismuth and copper is precipitated completely by
ammonia which separates it from copper. Finally the active substance remains with bismuth.

We have not yet found any exact procedure for separating the active substance from bismuth by a wet
method. We have, however, effected incomplete separations as judged by the following facts:

When the sulphides are dissolved by nitric acid, the least soluble portions are the least active. In the
precipitation of the salts from water the first portions precipitated are by far the most active. We have
observed that on heating pitchblende one obtains by sublimation some very active products. This
observation led us to a separation process based on the difference in volatility between the active
sulphide and bismuth sulphide. The sulphides are heated in vacuum to about 700° in a tube of
Bohemian glass. The active sulphide is deposited in the form of a black coating in those regions of the
tube which are at 250° to 300°, while the bismuth sulphide stays in the hotter parts.

More and more active products are obtained by repetition of these different operations. Finally we
obtained a substance whose activity is about four hundred times greater than that of uranium. We have
sought again among the known substances to determine if this is the most active. We have examined
compounds of almost all the elementary substances; thanks to the kindness of several chemists we have
had samples of the rarest substances. Uranium and thorium only are naturally active, perhaps tantalum
may be very feebly so.

We believe therefore that the substance which we have removed from pitchblende contains a metal not
yet reported close to bismuth in its analytical properties. If the existence of this new metal is confirmed,
we propose to call it polonium from the name of the country of origin of one of us.

M. Demarçay has been kind enough to examine the spectrum of the substance which we studied. He
was not able to distinguish any characteristic line apart from those ascribable to impurities. This fact is
not favourable to the idea of the existence of a new metal. However, M. Demarçay called our attention
to the fact that uranium, thorium, and tantalum exhibit spectra formed of innumerable very fine lines
difficult to resolve.[3,4]

Allow us to note that if the existence of a new element is confirmed, this discovery will be uniquely
attributable to the new method of detection that Becquerel rays provide.

--------------------------------------------------------------------------------
[1]This work was done at the Municipal School of Industrial Physics and Chemistry. We particularly
thank M. Bémont, head of chemical operations, for his advice and the assistance he willingly provided.
--original note
[2]Mme. P. Curie, Comptes Rendus, vol. 126, p. 1101. --original note

[3]The peculiarity of these three spectra is described in the fine work of M. Demarçay, Electric Spectra
(1895). --original note
[4]The excerpt in Boorse and Motz ends here. The remainder of the paper was translated by Carmen
Giunta, as were the original footnotes.--CJG

--------------------------------------------------------------------------------
Back to the list of selected historical papers.
Back to the top of Classic Chemistry.Ernest Rutherford (1871-1937) & Frederick Soddy (1877-1956)
The Cause and Nature of Radioactivity
from Philosophical Magazine 4, 370-96 (1902) [as abridged and reprinted in Henry A. Boorse & Lloyd
Motz, The World of the Atom, Vol. 1 (New York: Basic Books, 1966)]

Introduction
The following papers give the results of a detailed investigation of the radioactivity of thorium
compounds which has thrown light on the questions connected with the source and maintenance of the
energy dissipated by radioactive substances. Radioactivity is shown to be accompanied by chemical
changes in which new types of matter are being continuously produced. These reaction products are at
first radioactive, the activity diminishing regularly from the moment of formation. Their continuous
production maintains the radioactivity of the matter producing them at a definite equilibrium-value.
The conclusion is drawn that these chemical changes must be sub-atomic in character.
The present researches had as their starting-point the facts that had come to light with regard to thorium
radioactivity. Besides being radioactive in the same sense as the uranium compounds, the compounds
of thorium continuously emit into the surrounding atmosphere a gas which it has been named, is the
source of rays, which ionize gases and darken the photographic film.[1]

The most striking property of the thorium emanation is its power of exciting radioactivity on all
surfaces with which it comes into contact. A substance after being exposed for some time in the
presence of the emanation behaves as if it were covered with an invisible layer of an intensely active
material. If the thoria is exposed in a strong electric field, the excited radioactivity is entirely confined
to the negatively charged surface. In this way it is possible to concentrate the excited radioactivity on a
very small area. The excited radioactivity can be removed by rubbing or by the action of acids, as, for
example, sulphuric, hydrochloric, and hydrofluoric acids. If the acids be then evaporated, the
radioactivity remains on the dish.

The emanating power of thorium compounds is independent of the surrounding atmosphere, and the
excited activity it produces is independent of the nature of the substance on which it is manifested.
These properties made it appear that both phenomena were caused by minute quantities of special kinds
of matter in the radioactive state, produced by the thorium compound.
The next consideration in regard to these examples of radioactivity, is that the activity in each case
diminishes regularly with the lapse of time, the intensity of radiation at each instant being proportional
to the amount of energy remaining to be radiated. For the emanation a period of one minute, and for the
excited activity a period of eleven hours, causes the activity to fall to half its value. ... The radioactivity
of thorium at any time is the resultant of two opposing processes--

The production of fresh radioactive material at a constant rate by the thorium compound;
The decay of the radiating power of the active material with time.
The normal or constant radioactivity possessed by thorium is an equilibrium value, where the rate of
increase of radioactivity due to the production of fresh active material is balanced by the rate of decay
of radioactivity of that already formed. It is the purpose of the present paper to substantiate and
develope this hypothesis.

The Rates of Recovery and Decay of Thorium Radioactivity


A quantity of the pure thorium nitrate was separated from ThX ... by several precipitations with
ammonia. The radioactivity of the hydroxide so obtained was tested at regular intervals to determine
the rate of recovery of its activity. For this purpose the original specimen of .5 gram was left
undisturbed throughout the whole series of measurements on the plate over which it had been sifted,
and was compared always with .5 gram of ordinary de-emanated thorium oxide spread similarly on a
second plate and also left undisturbed. The emanation from the hydroxide was prevented from
interfering with the results by a special arrangement for drawing a current of air over it during the
measurements.
The active filtrate from the preparation was concentrated and made up to 100 c.c. volume. One quarter
was evaporated to dryness and the ammonium nitrate expelled by ignition in a platinum dish, and the
radioactivity of the residue tested at the same intervals as the hydroxide to determine the rate of decay
of its activity. The comparison in this case was a standard sample of uranium oxide kept undisturbed on
a metal plate, which repeated work has shown to be a perfectly constant source of radiation. The
remainder of the filtrate was used for other experiments.

The following table gives an example of one of a numerous series of observations made with different
preparations at different times. The maximum value obtained by the hydroxide and the original value of
the ThX are taken as 100: Time in days Activity of Hydroxide Activity of ThX
0 44 100
1 37 117
2 48 100
3 54 88
4 62 72
5 68 --
6 71 53
8 78 --
9 -- 29.5
10 83 25.2
13 -- 15.2
15 -- 11.1
17 96.5 --
21 99 --
28 100 --

[Figure 1] shows the curves obtained by plotting the radioactivities as the ordinates, and the time in
days as abscissae. Curve II. illustrates the rate of recovery of the activity of thorium, curve I. the rate of
decay of the activity of ThX. It will be seen that neither of the curves is regular for the first two days.
The activity of the hydroxide at first actually diminished and was at the same value after two days as
when first prepared. The activity of the ThX, on the other hand, at first increases and does not begin to
fall below the original value till after the lapse of two days. ... These results cannot be ascribed to errors
of measurement, for they have been regularly observed whenever similar preparations have been tested.
The activity of the residue obtained from thorium oxide by the second method of washing decayed very
similarly to that of ThX, as shown by the above curve.

If for present purposes the initial periods of the curve are disregarded and the later portions only
considered, it will be seen at once that the time taken for the hydroxide to recover one half of its lost
activity is about equal to the time taken by the ThX to lose half its activity, viz., in each case about 4
days, and speaking generally the percentage proportion of the lost activity regained by the hydroxide
over any given interval is approximately equal to the percentage proportion of the activity lost by the
ThX during the same interval. If the recovery curves is produced backwards in the normal direction to
cut the vertical axis, it will be seen to do so at a minimum of about 25 per cent., and the above result
holds even more accurately if the recovery is assumed to start from this constant minimum, as indeed,
it has been shown to do under suitable conditions. ...

This is brought out by [Figure 2], which represents the recovery curve of thorium in which the
percentage amounts of activity recovered, reckoned from this 25 per cent. minimum, are plotted as
ordinates. In the same figure the decay curve after the second day is shown on the same scale.

The activity of ThX decreases very approximately in a geometrical progression with the time, i.e. if I0
represent the initial activity and It the activity after time t, (1) It/I0 = e-lt ,
where l is a constant and e the base of natural logarithms.

The experimental curve obtained with the hydroxide for the rate of rise of its activity from a minimum
to a maximum value will therefore be approximately expressed by the equation (2) It/I0 = 1- e-lt ,
where I0 represents the amount of activity recovered when the maximum is reached, and It the activity
recovered after time t, l being the same constant as before.

Now this last equation has been theoretically developed in other places to express the rise of activity to
a constant maximum of a system consisting of radiating particles in which

The rate of supply of fresh radiating particles is constant.


The activity of each particle dies down geometrically with the time according to equation (1).
It therefore follows that if the initial irregularities of the curves are disregarded and the residual activity
of thorium is assumed to possess a constant value, the experimental curve obtained for the recovery of
activity will be explained if two processes are supposed to be taking place:

That the active constituent ThX is being produced at a constant rate;


That the activity of the ThX decays geometrically with time.
Without at first going into the difficult questions connected with the initial irregularities and the
residual activity, the main result that follows from the curves given can be put to experimental test very
simply. The primary conception is that the major part of the radioactivity of thorium is not due to the
thorium at all, but to the presence of a non-thorium substance in minute amount which is being
continuously produced.

Chemical Properties of ThX


The fact that thorium on precipitation from its solutions by ammonia leaves the major part of its
activity in the filtrate does not of itself prove that a material constituent responsible for this activity has
been chemically separated. It is possible that the matter constituting the non-thorium part of the
solution is rendered temporarily radioactive by its association with thorium, and this property is
retained through the processes of precipitation, evaporation, and ignition, and manifests itself finally on
the residue remaining.
This view, however, can be shown to be quite untenable, for upon it any precipitate capable of
removing thorium completely from its solution should yield active residues similar to those obtained
from ammonia. Quite the reverse, however, holds.

When thorium nitrate is precipitated by sodium or ammonium carbonate, the residue from the filtrate
by evaporation and ignition is free from activity, and the thorium carbonate possesses the normal value
for its activity.

The same holds true when oxalic acid is used as the precipitant. This reagent even in strongly acid
solution precipitates almost all of the thorium. When the filtrate is rendered alkaline by ammonia,
filtered, evaporated, and ignited, the residue obtained is inactive.
In the case where sodium phosphate is used as the precipitant in ordinary acid solution, the part that
comes don is more or less free from ThX. On making the solution alkaline with ammonia, the
remainder of the thorium is precipitated as phosphate, and carries with it the whole of the active
constituent, so that the residue from the filtrate is again inactive.

In fact ammonia is the only reagent of those tried capable of separating ThX from thorium.

The result of Sir William Crookes with uranium, which we have confirmed with the electrical method,
may be here mentioned. UrX is completely precipitated by ammonia together with uranium, and the
residue obtained by the evaporation of the filtrate is quite inactive.

There can thus be no question that both ThX and UrX are distinct types of matter with definite
chemical properties. Any hypothesis that attempts to account for the recovery of activity of thorium and
uranium with time must of necessity start from this primary conception.

The Continuous Production of ThX


If the recovery of the activity of thorium with time is due to the production of ThX, it should be
possible to obtain experimental evidence of the process. The first point to be ascertained is how far the
removal of ThX by the method given reduces the total radioactivity of thorium. A preliminary trial
showed that the most favourable conditions for the separation are by precipitating in hot dilute
solutions by dilute ammonia. A quantity of 5 grams of thorium nitrate, as obtained from the maker, was
so precipitated by ammonia, the precipitate being redissolved in nitric acid and reprecipitated under the
same conditions successively without lapse of time.
The removal of ThX was followed by measuring the activity of the residues obtained from the first
filtrate was equivalent to 4.25 grams of thoria, from the second to 0.33 gram, and from the third to 0.07
gram. It will be seen that by two precipitations practically the whole of the ThX is removed. The
radioactivity of the separated hydroxide was 48 per cent. of that of the standard de-emanated sample of
thoria.

Rate of Production of ThX


A quantity of thorium nitrate solution that had been freed from ThX about a month before, was again
subjected to the same process. The activity of the residue from the filtrate in an experiment in which 10
grams of this nitrate had been employed was equivalent to 8.3 grams of thorium oxide. This experiment
was performed on the same day as the one recorded above, in which 5 grams of new nitrate had been
employed, and it will be seen that there is no difference in the activity of the filtrate in the two cases. In
one month the activity of the ThX in a thorium compound again possesses its maximum value.

If a period of 24 hours is allowed to elapse between the successive precipitations, the activity of the
ThX formed during that time corresponds to about one-sixth of the maximum activity of the total
thorium employed. In three hours the activity of the amount produced is about one-thirtieth. The rate of
production of ThX worked out from those figures well agrees with the form of the curve obtained for
the recovery of activity of thorium, if the latter is taken to express the continuous production of ThX at
a constant rate and the diminution of the activity of the product in geometrical progression with time.

By using the sensitive electrometer, the course of production of ThX can be followed after extremely
short intervals. Working with 10 grams of thorium nitrate, the amount produced in the minimum time
taken to carry out the successive precipitations is as much as can be conveniently measured. If any
interval is allowed to lapse the effect is beyond the range of the instrument, unless the sensitiveness is
reduced to a fraction of its ordinary value by the introduction of capacities into the system. Capacities
of .01 and .02 microfarad, which reduce the sensitiveness to less than one two-hundredth of the normal,
were frequently employed in dealing with these active residues.

The process of the production of ThX is continuous, and no alteration was observed in the amount
produced in a given time after repeated separations. In an experiment carried out for another purpose
after 23 successive precipitations extending over 9 days, the amount formed during the last interval was
as far as could be judged no less than what occurred at the beginning of the process.

The phenomena of radioactivity, by means of the electrometer as its measuring instrument, thus enables
us to detect and measure changes occurring in matter after a few minutes' interval, which have never
yet been detected by the balance or suspected of taking place.

The Cause and Nature of Radioactivity


The foregoing conclusions enable a great generalization to be made in the subject of radioactivity.
Energy considerations require that the intensity of radiation from any source should die down with time
unless there is a constant supply of energy to replace that dissipated. This has been found to hold true in
the case of all known types of radioactivity with the exception of the "naturally" radioactive elements--
to take the best established cases, thorium, uranium, and radium. It will be shown later that the
radioactivity of the emanation produced by thorium compounds decays geometrically with the time
under all conditions, and is not affected by the most drastic chemical and physical treatment. The same
has been shown by one of us to hold for the excited radioactivity produced by the thorium emanation.
This decays at the same rate whether on the wire on which it is originally deposited, or in solution of
hydrochloric or nitric acid. The excited radioactivity produced by the radium emanation appears
analogous. All these examples satisfy energy considerations. In the case of the three naturally occurring
radioactive elements, however, it is obvious that there must be a continuous replacement of the
dissipated energy, and no satisfactory explanation has yet been put forward.
The nature of the process becomes clear in the light of the foregoing results. The material constituent
responsible for the radioactivity, when it is separated from the thorium which produces it, then behaves
in the same way as the other types of radioactivity cited. Its activity decays geometrically with the time,
and the rate of decay is independent of the molecular conditions. The normal radioactivity is, however,
maintained at a constant value by a chemical change which produces fresh radioactive material at a rate
also independent of the conditions. The energy required to maintain the radiations will be accounted for
if we suppose that the energy of the system after the change has occurred is less than it was before.

The work of Crookes and Becquerel on the separation of UrX and the recovery of the activity of the
uranium with time, makes it appear extremely probable that the same explanation holds true for this
element. The work of M. and Mme. Curie, the discoverers of radium, goes to show that this body easily
suffers a temporary decrease of its activity by chemical treatment, the normal value being regained
after the lapse of time, and this can be well interested on the new view. All known types of radioactivity
can thus be brought under the same category.

Summary of Results
The foregoing experimental results may be briefly summarized. The major part of the radioactivity of
thorium--ordinarily about 54 percent.--is due to a non-thorium type of matter, ThX, possessing distinct
chemical properties, which is temporarily radioactive, its activity falling to half value in about four
days. The constant radioactivity of thorium is maintained by the production of this material at a
constant rate. Both the rate of production of the new material and the rate of decay of its activity appear
to be independent of the physical and chemical condition of the system.
The ThX further possesses the property of exciting radioactivity on surrounding inactive matter, and
about 21 per cent. of the total activity under ordinary circumstances is derived from this source. Its rate
of decay and other considerations make it appear probable that it is the same as the excited
radioactivity produced by the thorium emanation, which is in turn produced by ThX . There is evidence
that, if from any cause the emanation is prevented from escaping in the radioactive state, the energy of
its radiation goes to augment the proportion of excited radioactivity in the compound.

[The sections on which the following conclusions were based have been omitted. --Boorse & Motz.]

Thorium can be freed by suitable means from both ThX and the excited radioactivity which the latter
produces, and then possesses an activity about 25 per cent. of its original value, below which it has not
been reduced. This residual radiation consists entirely of rays non-deviable by the magnetic field,
whereas the other two components comprise both deviable and non-deviable radiation. Most probably
this residual activity is caused by a second non-thorium type of matter produced in the same change as
ThX, and it should therefore prove possible to separate it by chemical methods.

General Theoretical Considerations


Turning from the experimental results to their theoretical interpretation, it is necessary to first consider
the generally accepted view of the nature of radioactivity. It is well established that this property is the
function of the atom and not of the molecule. Uranium and thorium, to take the most definite cases,
possess the property in whatever molecular condition they occur, and the former also in the elementary
state. So far as the radioactivity of different compounds of different density and states of division can
be compared together, the intensity of the radiation appears to depend only on the quantity of active
element present. It is not possible to explain the phenomena by the existence of impurities associated
with the radioactive elements, even if any advantage could be derived from the assumption. For these
impurities must necessarily be present always to the same extent in different specimens derived from
the most widely different sources, and, moreover, they must persist in altered amount after the most
refined processes of purification. This is contrary to the accepted meaning of the term impurity.
All the most prominent workers in this subject are agreed in considering radioactivity an atomic
phenomenon. M. and Mme. Curie, the pioneers in the chemistry of the subject, have recently put
forward their views. They state that this idea underlies their whole work fro the beginning and created
their methods of research. M. Becquerel, the original discoverer of the property for uranium, in his
announcement of the recovery of the activity of the same element after the active constituent had been
removed by chemical treatment, points out the significance of the fact that uranium is giving out
cathode-rays. These, according to the hypothesis of Sir William Crookes and Prof. J. J. Thomson, are
material particles of mass one thousandth of the hydrogen atom.

Since, therefore, radioactivity is at once an atomic phenomenon and accompanied by chemical changes
in which new types of matter are produced, these changes must be occurring within the atom, and the
radioactive elements must be undergoing spontaneous transformation. The results that have so far been
obtained, which indicate that the velocity of the reaction is unaffected by the conditions, make it clear
that the changes in question are different in character from any that have been before dealt with in
chemistry. It is apparent that we are dealing with phenomena outside the sphere of known atomic
forces. Radioactivity may therefore be considered as a manifestation of subatomic chemical change.

The changes brought to knowledge by radioactivity, although undeniably material and chemical in
nature, are of a different order of magnitude from any that have before been dealt with in chemistry.
The course of the production of new matter which can be recognized by the electrometer, by means of
the property of radioactivity, after the lapse of a few hours or even minutes, might conceivably require
geological epochs to attain to quantities recognized by the balance. However, the well-defined chemical
properties of both ThX and UrX are not in accordance with the view that the actual amounts involved
are of this extreme order of minuteness. On the other hand, the existence of radioactive elements at all
in the earth's crust is an à priori argument against the magnitude of the change being anything but
small.

Radioactivity as a new property of matter capable of exact quantitative determination thus possesses an
interest apart from the peculiar properties and powers which the radiations themselves exhibit. Mme.
Curie, who isolated from pitchblende a new substance, radium, which possessed distinct chemical
properties and spectroscopic lines, used the property as a means of chemical analysis. An exact parallel
is to be found in Bunsen's discovery and separation of caesium and rubidium by means of the
spectroscope.

The present results show that radioactivity can also be used to follow chemical changes occurring in
matter. The properties of matter that fulfil the necessary conditions for the study of chemical change
without disturbance to the reacting system are few in number. It seems not unreasonable to hope, in the
light of the foregoing results, that radioactivity, being such a property, affords the means of obtaining
information of the processes occurring within the chemical atom, in the same way as the rotation of the
plane of polarization and other physical properties have been used in chemistry for the investigation of
the course of molecular change.

--------------------------------------------------------------------------------
[1]If thorium oxide be exposed to a white heat its power of giving an emanation is to a large extent
destroyed. Thoria that has been so treated is referred to throughout as "de-emanated."
--------------------------------------------------------------------------------
Back to the list of selected historical papers.
Back to the top of Classic Chemistry.Antoine Henri Becquerel (1852-1908)
On the rays emitted by phosphorescence
[read before the French Academy of Science 24 Feb. 1896 (Comptes Rendus 122, 420 (1896))
translated by Carmen Giunta]
In an earlier session, M. Chairman Henry announced that phosphorescent zinc sulfide placed in the
path of rays emanating from a Crookes tube augmented the intensity of rays passing through the
aluminum.

Elsewhere, M. Niewenglowski recognized that commercial phosphorescent calcium sulfide emits rays
which pass through opaque bodies.

This fact extends to various phosphorescent bodies, and in particular to uranium salts whose
phosphorescence has a very brief duration.

With the double sulfate of uranium and potassium, of which I have a few crystals forming a thin
transparent crust, I was able to perform the following experiment:

One wraps a Lumière photographic plate with a bromide emulsion in two sheets of very thick black
paper, such that the plate does not become clouded upon being exposed to the sun for a day.

One places on the sheet of paper, on the outside, a slab of the phosphorescent substance, and one
exposes the whole to the sun for several hours. When one then develops the photographic plate, one
recognizes that the silhouette of the phosphorescent substance appears in black on the negative. If one
places between the phosphorescent substance and the paper a piece of money or a metal screen pierced
with a cut-out design, one sees the image of these objects appear on the negative.

One can repeat the same experiments placing a thin pane of glass between the phosphorescent
substance and the paper, which excludes the possibility of chemical action due to vapors which might
emanate from the substance when heated by the sun's rays.

One must conclude from these experiments that the phosphorescent substance in question emits rays
which pass through the opaque paper and reduces silver salts.
--------------------------------------------------------------------------------

On the invisible rays emitted by phosphorescent bodies.


[read before the French Academy of Science 2 March 1896 (Comptes Rendus 122, 501 (1896))
translated by Carmen Giunta]
In the previous session, I summarized the experiments which I had been led to make in order to detect
the invisible rays emitted by certain phosphorescent bodies, rays which pass through various bodies
that are opaque to light.

I was able to extend these observations, and although I intend to continue and to elaborate upon the
study of these phenomena, their outcome leads me to announce as early as today the first results I
obtained.

The experiments which I shall report were done with the rays emitted by crystalline crusts of the
double sulfate of uranyl and potassium [SO4(UO)K+H2O], a substance whose phosphorescence is very
vivid and persists for less than 1/100th of a second. The characteristics of the luminous rays emitted by
this material have been studied previously by my father, and in the meantime I have had occasion to
point out some interesting peculiarities which these luminous rays manifest.

One can confirm very simply that the rays emitted by this substance, when it is exposed to sunlight or
to diffuse daylight, pass through not only sheets of black paper but also various metals, for example a
plate of aluminum and a thin sheet of copper. In particular, I performed the following experiment:

A Lumière plate with a silver bromide emulsion was enclosed in an opaque case of black cloth,
bounded on one side by a plate of aluminum; if one exposed the case to full sunlight, even for a whole
day, the photographic plate would not become clouded; but, if one came to attach a crust of the uranium
salt to the exterior of the aluminum plate, which one could do, for example, by fastening it with strips
of paper, one would recognize, after developing the photographic plate in the usual way, that the
silhouette of the crystalline crust appears in black on the sensitive plate and that the silver salt facing
the phosphorescent crust had been reduced. If the layer of aluminum is a bit thick, then the intensity of
the effect is less than that through two sheets of black paper.

If one places between the crust of the uranium salt and the layer of aluminum or black paper a screen
formed of a sheet of copper about 0.10 mm thick, in the form of a cross for example, then one sees in
the image the silhouette of that cross, a bit fainter yet with a darkness indicative nonetheless that the
rays passed through the sheet of copper. In another experiment, a thinner sheet of copper (0.04 mm)
attenuated the active rays much less.

Phosphorescence induced no longer by the direct rays of the sun, but by solar radiation reflected in a
metallic mirror of a heliostat, then refracted by a prism and a quartz lens, gave rise to the same
phenomena.
I will insist particularly upon the following fact, which seems to me quite important and beyond the
phenomena which one could expect to observe: The same crystalline crusts, arranged the same way
with respect to the photographic plates, in the same conditions and through the same screens, but
sheltered from the excitation of incident rays and kept in darkness, still produce the same photographic
images. Here is how I was led to make this observation: among the preceding experiments, some had
been prepared on Wednesday the 26th and Thursday the 27th of February, and since the sun was out
only intermittently on these days, I kept the apparatuses prepared and returned the cases to the darkness
of a bureau drawer, leaving in place the crusts of the uranium salt. Since the sun did not come out in the
following days, I developed the photographic plates on the 1st of March, expecting to find the images
very weak. Instead the silhouettes appeared with great intensity. I immediately thought that the action
had to continue in darkness, and I arranged the following experiment:

At the bottom of a box of opaque cardboard I placed a photographic plate; then, on the sensitive side I
put a crust of the uranium salt, a convex crust which only touched the bromide emulsion at a few
points; then, alongside, I placed on the same plate another crust of the same salt but separated from the
bromide emulsion by a thin pane of glass; this operation was carried out in the darkroom, then the box
was shut, then enclosed in another cardboard box, and finally put in a drawer.

I did the same with the case closed by a plate of aluminum in which I put a photographic plate and then
on the outside a crust of the uranium salt. The whole was enclosed in an opaque box, and then in a
drawer. After five hours, I developed the plates, and the silhouettes of the crystalline crusts appeared in
black as in the previous experiments and as if they had been rendered phosphorescent by light. For the
crust placed directly on the emulsion, there was scarcely a difference in effect between the points of
contact and the parts of the crust which remained about a millimeter away from the emulsion; the
difference can be attributed to the different distance from the source of the active rays. The effect from
the crust placed on a pane of glass was very slightly attenuated, but the shape of the crust was very well
reproduced. Finally, through the sheet of aluminum, the effect was considerably weaker, but
nonetheless very clear.

It is important to observe that it appears this phenomenon must not be attributed to the luminous
radiation emitted by phosphorescence, since at the end of 1/100th of a second this radiation becomes so
weak that it is hardly perceptible any more.

One hypothesis which presents itself to the mind naturally enough would be to suppose that these rays,
whose effects have a great similarity to the effects produced by the rays studied by M. Lenard and M.
Röntgen, are invisible rays emitted by phosphorescence and persisting infinitely longer than the
duration of the luminous rays emitted by these bodies. However, the present experiments, without
being contrary to this hypothesis, do not warrant this conclusion. I hope that the experiments which I
am pursuing at the moment will be able to bring some clarification to this new class of phenomena.

--------------------------------------------------------------------------------
Back to the list of selected historical papers.
Back to the top of Classic Chemistry.

Selected Classic Papers


from the

History of Chemistry
The nucleus: isotopes and radioactivity
• Corbin Allardice and Edward R. Trapnell (1949): An eyewitness account of the first self-
sustaining nuclear chain reaction. This paper is at the ChemTeam site.
• Francis Aston (1919): early report of mass spectra, suggesting that isotopes have integer masses.
(Link to a photo of his apparatus or biographical sketch of Aston.)
• Francis Aston (1920): early report of mass spectra showing isotopes of stable elements. This
paper is at the ChemTeam site, as is this picture.
• Henri Becquerel: two brief reports about radioactivity read to the French Academy of Sciences
one week apart in 1896. In between the two reports, Becquerel realized that he was not dealing
with ordinary phosphorescence! (Link to a biographical sketch of Becquerel and view a picture
of a photographic plate from which he made his discovery.
• Niels Bohr (1939): liquid drop model of fission in wake of Meitner-Frisch paper. This paper is
at the ChemTeam site.
• Harriet Brooks: 1904 description of a volatile radioactive product from radium: Marie Curie
was not the only woman active in early research on radioactivity! This paper is at the UCLA site
on contributions of women to physics, as is this biographical information on Brooks.
• James Chadwick: 1932 letter and subsequent detailed paper explaining experimental
observations by invoking a new particle, the neutron. These papers are at the ChemTeam site.
(View part of his apparatus or biographical information on Chadwick.)
• John Cockcroft and Ernest Walton: 1932 paper on the disintegration of lithium by fast protons:
artificial transmutation. This paper is at Nature's physics portal. (Link to a biographical sketch
of Cockcroft and one of Walton.)
• Marie Curie: 1898 paper surveying the material world for radioactivity, finding it in uranium
and thorium minerals, and suggesting that a new radioactive element may be found in
pitchblende. (Link to a biographical information on Curie.)
• Pierre and Marie Curie: 1898 announcement of a new radioactive element, polonium.
• Pierre and Marie Curie and G. Bémont: December 1898 announcement of a new strongly
radioactive element, radium.
• Kasimir Fajans: 1913 paper on the radioactive displacement law and isotopes. This paper is at
the ChemTeam site as is this photo.
• Enrico Fermi: 1934 note suspects (incorrectly) production of transuranic elements by
bombarding thorium and uranium with neutrons. Noddack critiqued this conclusion on chemical
grounds. Meitner and Frisch later explained these results as nuclear fission. Fermi's paper is at
the ChemTeam site. View biographical information on Fermi.
• Otto Frisch: brief 1939 note follows up paper with Lise Meitner on fission of uranium This
paper is at the ChemTeam site. View a biographical sketch of Frisch.
• Hans Geiger and Ernest Marsden: 1909 paper reporting unexpected backscatter of alpha
particles; interpretation of this phenomenon led to the nuclear model of the atom. This paper is
at the ChemTeam site. (Link to a biographical sketch of Geiger
• Hans Geiger: from 1910 paper on scattering of alpha particles from gold foil. This paper is at
the ChemTeam site.
• Hans Geiger and Ernest Marsden: 1913 paper comparing backscatter of alpha particles to the
predictions of Rutherford's nuclear model of the atom. This paper is at the ChemTeam site.
• Otto Hahn and Fritz Strassmann: 1939 paper reporting a result they barely believe themselves:
barium, lanthanum, and cerium obtained from the bombardment of uranium by neutrons, then a
more definite announcement of uranium fission. These papers are at the ChemTeam site. View
biographical information on Hahn and Strassmann
• Lise Meitner and Otto Frisch: 1939 paper invokes fission of uranium to explain neutron
bombardment results. This paper is at the Nature's physics portal. Link to a biographical sketch
of Meitner.
• Ida Noddack: 1934 note critiques Fermi's conclusion that he had produced transuranic elements
by bombarding thorium and uranium with neutrons. Noddack's paper is at the ChemTeam site.
Link to biographical information on Noddack.
• William Ramsay & Frederick Soddy: 1903 investigation of the inert nature of radium emanation
and the observation that helium is evolved from both radium and its emanation.
• Theodore W. Richards & Max E. Lembert: 1914 paper on atomic weights of lead found
different atomic weights for lead of radioactive origin compared to "ordinary" lead; authors
cautiously interpret the results as consistent with the concept of isotopes. Link to a biographical
sketch of Richards.
• Wilhelm Röntgen: "On a New Kind of Rays", 1895 paper first describing X-rays. X-ray
photographs of a human hand (fig. 1) and a compass card (fig. 2) accompanied the paper. [More
information about Röntgen and X-rays: The New Light: Discovery and Introduction]
• Ernest Rutherford: 1899 paper distinguishes between two types of radioactivity, which he labels
alpha and beta. This paper is at the ChemTeam site. (Link to a biographical sketch Rutherford.)
• Ernest Rutherford: 1900 paper introduces concept of radioactive half-life and measures half-life
of "thorium emanation" (now known as 220Rn). This paper is at the ChemTeam site.
• Ernest Rutherford & Frederick Soddy: 1902 paper that concludes, "radioactive elements must
be undergoing spontaneous transformation." (This conclusion is found in the paper's final
section.)
• Ernest Rutherford and T. Royds: 1909 paper identifying the α particle with doubly-charged
helium. The paper is worth reading for the careful marshalling of one last conclusive piece of
evidence about the nature of the particles Rutherford and his co-workers had been studying for a
decade.
• Ernest Rutherford: abstract of a 1911 paper proposing the nuclear model of the atom to explain
results of scattering experiments. This paper is at the ChemTeam site.
• Ernest Rutherford: 1911 paper proposing the nuclear model of the atom to explain results of
scattering experiments. This paper is at the ChemTeam site.
• Ernest Rutherford: 1914 paper on the nuclear model of the atom, including reference to
Moseley's work on atomic number. This paper is at the ChemTeam site, as is Moseley's.
• Ernest Rutherford: 1919 paper describing the bombardment of nitrogen by alpha particles.
Rutherford concludes the nitrogen atoms are disintegrated in the process. So atoms are not
indestructable after all, and the alchemists' dreams of transmutation are realized.
• Ernest Rutherford: 1920 lecture describing the state of knowledge of nuclear structure at a time
after the discovery of isotopy and atomic number but before the neutron; the standard picture
included electrons in the nucleus.
• M. L. Oliphant, P. Harteck, and Ernest Rutherford: 1934 note from the Rutherford lab
describes fusion ('transmutation') of deuterium. These papers (preliminary note and more
detailed paper) are at the ChemTeam site.
• Frederick Soddy: 1913 paper which gives the rules for chemical transformations accompanying
α and β decay; its discussion of "non-separable" elements all but defines (but does not name)
isotopy, including a speculation that they are not limited to radioactive elements. (Link to a
biographical sketch of Soddy.)
• Frederick Soddy: 1913 paper which introduces the term "isotopes" for atoms which have the
same nuclear charge but different mass.
• Frederick Soddy: from 1913 review article; discusses isotopes and the displacement law
• Silvanus Thompson: Thompson thought of performing the same sorts of experiments as
Becquerel at about the same time; comparison of this paper with Becquerel's highlights the luck
and genius of Becquerel. This article also illustrates the confusion immediately following the
discovery of X-rays and radioactivity: the former were not believed to be electromagnetic and
the latter was!
• Harold Urey, Ferdinand Brickwedde, and George Murphy: 1932 paper announcing detection of
a heavy isotope of hydrogen, H2 (reprinted with permission of the American Physical Society).
View biographical sketches of Urey, Brickwedde, and Murphy.

Organic chemistry
• Jean-Baptiste-André Dumas: paper on acetic acid and trichloroacetic acid (1839) supporting
Dumas' notion of chemical types. Link to a biographical sketch of Dumas.
• Jean-Baptiste-André Dumas and Justus von Liebig (1837): organic chemistry differs from
inorganic in that the radicals in the latter are simple, but in the former are compound. (View a
biographical sketch of Liebig.)
• Emil Fischer: 1891 paper on the structure of glucose and other simple sugars, a landmark of
stereochemical reasoning from wet chemistry. This paper [pdf] is at J. Michael McBride's site at
Yale. Link to a biographical sketch of Fischer.
• Edward Frankland: complete 1852 paper on organometallic compounds; it contains an early and
clear statement of the concept of valence. (Thanks to John Park for transcription.) Link to
further information on Frankland.
• Charles Gerhardt: 1853 excerpt on organic types. Link to biographical sketch of Gerhardt.
• August Wilhelm von Hofmann: 1851 excerpt on amines and organic ammonium compounds,
relevant to type theory. Link to a biographical sketch of Hofmann.
• August Kekule: excerpt of 1865 paper on the structure of aromatic compounds. This paper is on
Rod Beavon's chemistry site. (Link to further information on Kekule.)
• Joseph Achille Le Bel: tetrahedral geometry of carbon (1874). This paper is at the ChemTeam
site as is this photo.
• Jacobus van't Hoff: optical activity and the tetrahedral geometry of carbon (1874). This paper is
at the ChemTeam site. Link to a biographical sketch of van't Hoff.
• A. D. Walsh, R. Robinson, C. A. McDowell, and J.W. Linnett separately discuss Walsh's
proposed description of bonding in cyclopropane, 1947. These papers are at Daniel Berger's
Walsh cyclopropane pages at Bluffton College.
• Alexander Williamson: synthesis of ether and structure of ethers and alcohols (1850). Link to
further information about Williamson.
• Friedrich Wöhler: synthesis of urea from inorganic materials, conventionally regarded as fatal to
the idea that organic compounds could only be produced through a "vital force." This paper is at
the ChemTeam site, as is this picture.
• Charles-Adolphe Wurtz on amines and their relation to ammonia (1849). (Link to a photo of
Wurtz or a biographical paragraph.)

Periodic table and periodic law


• Humphry Davy: 1812 paper searching for analogies among elements.
• Johann Wolfgang Döbereiner: 1829 paper on triads of analogous elements and their
classification. Link to a biographical sketch of Döbereiner .
• Dmitrii Mendeleev, (1869): his first published periodic table and the abstract by which it was
first known in Western Europe. (Link to a collection of on-line material about Mendeleev.)
• Dmitrii Mendeleev, (1871): table from Annalen, suppl. VIII, 133 (1871). This item is posted at
Chris Heilman's Pictorial Periodic Table site.
• Dmitrii Mendeleev: excerpt from 1871 paper on periodicity of the elements focuses on the
properties of the predicted element eka-boron, now known as scandium. This paper is on Rod
Beavon's chemistry site.
• Dmitrii Mendeleev, (1889): Faraday lecture on the Periodic Law, 20 years after Mendeleev's
first work on the subject
• Julius Lothar Meyer, (1870). A table of most of the known elements arranged to show family
resemblances and a figure showing atomic volumes varying periodically. (Link to further
information on Meyer.)
• Julius Lothar Meyer: excerpt from 1870 paper on periodicity of the elements. This paper is on
Rod Beavon's chemistry site.
• Henry Moseley (1913, 1914): X-ray spectra of the elements reveal integers characteristic of
each element, namely the atomic number. This paper is at the ChemTeam site, as is this picture
and this essay on Moseley and his work.
• J. A. R. Newlands, (1863, 1864, 1865, and 1866): his first attempts to find relationships among
the atomic weights ("equivalents") of families of elements and accounts of his "law of octaves".
The 1863 and 1864 papers are a long way from the periodic table, and even from his later law of
octaves (1865 and 1866 items). (Link to a biographical sketch or view his picture in the Edgar
Fahs Smith collection.)
• J. A. R. Newlands, On the discovery of the periodic law: and on relations among the atomic
weights: 1884 monograph that collects all of Newlands' papers on the subject (This book is at
Google Books).
• William Ramsay, (1897): expands periodic table to make a new column for noble gases;
predicts discovery and properties of neon. (Link to a biographical sketch of Ramsay.)
• A. van den Broek: two letters on numbering the elements (1911 and 1913). These papers are at
the ChemTeam site: 1 and 2.
Thermodynamics
• Francis Bacon (1620): Before caloric and the kinetic theory, Bacon reviewed a wide range of
observations about heat and related phenomena to illustrate his inductive scientific method, and
suggested that heat is related to motion. There is even a mention of triboluminescent candy (in
Table II, number 11). (Link to a biographical sketch of Bacon or to a complete text of Novum
Organum.)
• Joseph Black: 1803 (posthumous) paper on heat distinguished between heat and temperature
and described specific heat and latent heat, even though treating heat as matter.
• Sadi Carnot: Reflections on the Motive Power of Fire (or "of heat" as this translation has it),
1824. This book is at the on-line Steam Engine Library at the University of Rochester. (Link to
a biographical sketch of Carnot.)
• Rudolf Clausius: excerpts from two papers on entropy. The first (1850) notes that heat is not
indestructible, and examines how it can be converted to work with the flow of heat from a warm
body to a cold; the second (1865) coins the term entropy and states the second law of
thermodynamics. (Link to a biographical sketch of Clausius.)
• Rudolf Clausius: 1857 paper on the kinetic theory of gases; derives expressions for the pressure
of a gas based from analysis of collisions for average molecular speeds.
• John Dalton, excerpts from A New System of Chemistry (1808). Describes how heat (caloric)
was believed to combine with matter, especially gases. (See also Lavoisier excerpt in this
section.) Heat capacity of gases proposed to vary inversely with atomic weight (like law of
Dulong & Petit).
• Humphry Davy: from Davy's first scientific publication (1799), some insightful ideas and
dubious experiments on the nature of heat and friction. (Link to a biographical sketch of Davy.)
• Daniel Gabriel Fahrenheit: 1724 paper observing several liquids to boil at constant
temperatures. (Link to biographical information on Fahrenheit.)
• Cato Guldberg and Peter Waage: "Studier over Affiniteten", describing law of mass action to the
Norwegian Academy of Sciences and Letters in 1864. This paper is at the ChemTeam site, as is
this picture.
• Josiah Willard Gibbs: preface to Statistical Mechanics, published in 1902. This paper [pdf] is at
the American Institute of Physics website. (Link to biographical information on Gibbs.)
• John Herapath: excerpt of 1821 paper on kinetic theory of gases: heat is motion, and there need
not be repulsive forces between gaseous atoms. Link to biographical information on Herapath.
• Germain Henri Hess: 1840 paper on heats of reaction (Hess's law) This paper is at the
ChemTeam site. (Link to a biographical sketch of Hess.)
• James Prescott Joule: 1845 note on the relationship between heat and mechanical energy (the
mechanical equivalent of heat). This paper is at the ChemTeam site. (View Joule's apparatus, or
link to a biographical sketch of Joule.)
• James Prescott Joule: 1851 estimate of the speed of a gas molecule.
• Antoine Lavoisier: on caloric and its role in the three states of matter, from Elements of
Chemistry (1789)
• Antoine Lavoisier: Oeuvres, (Paris, 1862-1893, 6 vols.): page images at Panopticon Lavoisier
includes complete Traité élémentaire de chimie
• Henri Louis le Chatelier (1884): enunciates his principle concerning chemical equilibrium. Link
to a biographical sketch of le Chatelier
• James Clerk Maxwell: introduces Maxwell's "demon" and its implications for the second law of
thermodynamics (1872).
• Julius Robert Mayer: on the conservation or interconvertability of energy (or force or vis viva,
as the paper says). Click here for a biographical sketch of Mayer.
• Alexis-Thérèse Petit & Pierre-Louis Dulong: complete 1819 paper on heat capacities of
elements, that contains the law of Dulong & Petit. (Link to biographical information on Dulong
and Petit.)
• Agnes Pockels: letter on surface properties of water, sent to Lord Rayleigh and later published
in Nature. This paper is at the Contributions of 20th Century Women to Physics site at UCLA.
(Link to biographical information on Pockels.)
• François-Marie Raoult: 1882 paper on freezing point depression. (Link to biographical sketch of
Raoult.)
• François-Marie Raoult: 1887 paper on the lowering of vapor pressure.
• Benjamin Thomson (Count Rumford): 1798 paper on the quantity and nature of the heat
generated in boring a cannon. This paper is at the ChemTeam site. (Link to a biographical
sketch of Rumford.)
• William Thomson (Baron Kelvin of Largs): some thoughts (not all correct--see Keith J. Laidler,
The World of Physical Chemistry, pp. 99-100) on an absolute thermodynamic scale of
temperature (1848). (Link to a biographical sketch of Kelvin.)
• William Thomson (Baron Kelvin of Largs): 1852 formulation of the second law of
thermodynamics and description of an absolute temperature scale.
• William Thomson (Baron Kelvin of Largs) (1865): an application of heat transfer to geology,
leading Thomson to believe the earth is relatively young.
• Jacobus van't Hoff: osmosis and the analogy between solutions and gases (1887). This paper is
at the ChemTeam site.

Others
• Justus Liebig: Familiar Letters on Chemistry (1843). This monograph on chemistry and some
of its applications to agriculture and industry in the middle 19th century is available courtesy of
Peter Childs, Limerick, Ireland.
• Philosophical Transactions of the Royal Society, volumes 50-67 (1757-77). This resource is
available as page images at the Internet Library of Early Journals, Bodelian Library, Oxford
University. The entire volumes are posted, so this resource spans the range of natural
philosophy.
• Louis-Jacques Thenard: 1819 paper announces discovery of hydrogen peroxide and describes
some of its properties (including some painful tests: don't try this at home)

Back to the top of the classic papers list

Selected Classic
Papers
from the

History of Chemistry
The nucleus: isotopes and
radioactivity
• Corbin Allardice and Edward R.
Trapnell (1949): An eyewitness
account of the first self-sustaining
nuclear chain reaction. This paper is
at the ChemTeam site.
• Francis Aston (1919): early report of
mass spectra, suggesting that
isotopes have integer masses. (Link
to a photo of his apparatus or
biographical sketch of Aston.)
• Francis Aston (1920): early report of
mass spectra showing isotopes of
stable elements. This paper is at the
ChemTeam site, as is this picture.
• Henri Becquerel: two brief reports
about radioactivity read to the French
Academy of Sciences one week apart
in 1896. In between the two reports,
Becquerel realized that he was not
dealing with ordinary
phosphorescence! (Link to a
biographical sketch of Becquerel and
view a picture of a photographic
plate from which he made his
discovery.
• Niels Bohr (1939): liquid drop model
of fission in wake of Meitner-Frisch
paper. This paper is at the
ChemTeam site.
• Harriet Brooks: 1904 description of a
volatile radioactive product from
radium: Marie Curie was not the only
woman active in early research on
radioactivity! This paper is at the
UCLA site on contributions of
women to physics, as is this
biographical information on Brooks.
• James Chadwick: 1932 letter and
subsequent detailed paper explaining
experimental observations by
invoking a new particle, the neutron.
These papers are at the ChemTeam
site. (View part of his apparatus or
biographical information on
Chadwick.)
• John Cockcroft and Ernest Walton:
1932 paper on the disintegration of
lithium by fast protons: artificial
transmutation. This paper is at
Nature's physics portal. (Link to a
biographical sketch of Cockcroft and
one of Walton.)
• Marie Curie: 1898 paper surveying
the material world for radioactivity,
finding it in uranium and thorium
minerals, and suggesting that a new
radioactive element may be found in
pitchblende. (Link to a biographical
information on Curie.)
• Pierre and Marie Curie: 1898
announcement of a new radioactive
element, polonium.
• Pierre and Marie Curie and G.
Bémont: December 1898
announcement of a new strongly
radioactive element, radium.
• Kasimir Fajans: 1913 paper on the
radioactive displacement law and
isotopes. This paper is at the
ChemTeam site as is this photo.
• Enrico Fermi: 1934 note suspects
(incorrectly) production of
transuranic elements by bombarding
thorium and uranium with neutrons.
Noddack critiqued this conclusion on
chemical grounds. Meitner and
Frisch later explained these results as
nuclear fission. Fermi's paper is at
the ChemTeam site. View
biographical information on Fermi.
• Otto Frisch: brief 1939 note follows
up paper with Lise Meitner on
fission of uranium This paper is at
the ChemTeam site. View a
biographical sketch of Frisch.
• Hans Geiger and Ernest Marsden:
1909 paper reporting unexpected
backscatter of alpha particles;
interpretation of this phenomenon led
to the nuclear model of the atom.
This paper is at the ChemTeam site.
(Link to a biographical sketch of
Geiger
• Hans Geiger: from 1910 paper on
scattering of alpha particles from
gold foil. This paper is at the
ChemTeam site.
• Hans Geiger and Ernest Marsden:
1913 paper comparing backscatter of
alpha particles to the predictions of
Rutherford's nuclear model of the
atom. This paper is at the ChemTeam
site.
• Otto Hahn and Fritz Strassmann:
1939 paper reporting a result they
barely believe themselves: barium,
lanthanum, and cerium obtained
from the bombardment of uranium
by neutrons, then a more definite
announcement of uranium fission.
These papers are at the ChemTeam
site. View biographical information
on Hahn and Strassmann
• Lise Meitner and Otto Frisch: 1939
paper invokes fission of uranium to
explain neutron bombardment
results. This paper is at the Nature's
physics portal. Link to a biographical
sketch of Meitner.
• Ida Noddack: 1934 note critiques
Fermi's conclusion that he had
produced transuranic elements by
bombarding thorium and uranium
with neutrons. Noddack's paper is at
the ChemTeam site. Link to
biographical information on
Noddack.
• William Ramsay & Frederick Soddy:
1903 investigation of the inert nature
of radium emanation and the
observation that helium is evolved
from both radium and its emanation.
• Theodore W. Richards & Max E.
Lembert: 1914 paper on atomic
weights of lead found different
atomic weights for lead of
radioactive origin compared to
"ordinary" lead; authors cautiously
interpret the results as consistent
with the concept of isotopes. Link to
a biographical sketch of Richards.
• Wilhelm Röntgen: "On a New Kind
of Rays", 1895 paper first describing
X-rays. X-ray photographs of a
human hand (fig. 1) and a compass
card (fig. 2) accompanied the paper.
[More information about Röntgen
and X-rays: The New Light:
Discovery and Introduction]
• Ernest Rutherford: 1899 paper
distinguishes between two types of
radioactivity, which he labels alpha
and beta. This paper is at the
ChemTeam site. (Link to a
biographical sketch Rutherford.)
• Ernest Rutherford: 1900 paper
introduces concept of radioactive
half-life and measures half-life of
"thorium emanation" (now known as
220Rn). This paper is at the
ChemTeam site.
• Ernest Rutherford & Frederick
Soddy: 1902 paper that concludes,
"radioactive elements must be
undergoing spontaneous
transformation." (This conclusion is
found in the paper's final section.)
• Ernest Rutherford and T. Royds:
1909 paper identifying the α particle
with doubly-charged helium. The
paper is worth reading for the careful
marshalling of one last conclusive
piece of evidence about the nature of
the particles Rutherford and his co-
workers had been studying for a
decade.
• Ernest Rutherford: abstract of a 1911
paper proposing the nuclear model of
the atom to explain results of
scattering experiments. This paper is
at the ChemTeam site.
• Ernest Rutherford: 1911 paper
proposing the nuclear model of the
atom to explain results of scattering
experiments. This paper is at the
ChemTeam site.
• Ernest Rutherford: 1914 paper on the
nuclear model of the atom, including
reference to Moseley's work on
atomic number. This paper is at the
ChemTeam site, as is Moseley's.
• Ernest Rutherford: 1919 paper
describing the bombardment of
nitrogen by alpha particles.
Rutherford concludes the nitrogen
atoms are disintegrated in the
process. So atoms are not
indestructable after all, and the
alchemists' dreams of transmutation
are realized.
• Ernest Rutherford: 1920 lecture
describing the state of knowledge of
nuclear structure at a time after the
discovery of isotopy and atomic
number but before the neutron; the
standard picture included electrons in
the nucleus.
• M. L. Oliphant, P. Harteck, and
Ernest Rutherford: 1934 note from
the Rutherford lab describes fusion
('transmutation') of deuterium. These
papers (preliminary note and more
detailed paper) are at the ChemTeam
site.
• Frederick Soddy: 1913 paper which
gives the rules for chemical
transformations accompanying α and
β decay; its discussion of "non-
separable" elements all but defines
(but does not name) isotopy,
including a speculation that they are
not limited to radioactive elements.
(Link to a biographical sketch of
Soddy.)
• Frederick Soddy: 1913 paper which
introduces the term "isotopes" for
atoms which have the same nuclear
charge but different mass.
• Frederick Soddy: from 1913 review
article; discusses isotopes and the
displacement law
• Silvanus Thompson: Thompson
thought of performing the same sorts
of experiments as Becquerel at about
the same time; comparison of this
paper with Becquerel's highlights the
luck and genius of Becquerel. This
article also illustrates the confusion
immediately following the discovery
of X-rays and radioactivity: the
former were not believed to be
electromagnetic and the latter was!
• Harold Urey, Ferdinand Brickwedde,
and George Murphy: 1932 paper
announcing detection of a heavy
isotope of hydrogen, H2 (reprinted
with permission of the American
Physical Society). View biographical
sketches of Urey, Brickwedde, and
Murphy.

Organic chemistry
• Jean-Baptiste-André Dumas: paper
on acetic acid and trichloroacetic
acid (1839) supporting Dumas'
notion of chemical types. Link to a
biographical sketch of Dumas.
• Jean-Baptiste-André Dumas and
Justus von Liebig (1837): organic
chemistry differs from inorganic in
that the radicals in the latter are
simple, but in the former are
compound. (View a biographical
sketch of Liebig.)
• Emil Fischer: 1891 paper on the
structure of glucose and other simple
sugars, a landmark of stereochemical
reasoning from wet chemistry. This
paper [pdf] is at J. Michael
McBride's site at Yale. Link to a
biographical sketch of Fischer.
• Edward Frankland: complete 1852
paper on organometallic compounds;
it contains an early and clear
statement of the concept of valence.
(Thanks to John Park for
transcription.) Link to further
information on Frankland.
• Charles Gerhardt: 1853 excerpt on
organic types. Link to biographical
sketch of Gerhardt.
• August Wilhelm von Hofmann: 1851
excerpt on amines and organic
ammonium compounds, relevant to
type theory. Link to a biographical
sketch of Hofmann.
• August Kekule: excerpt of 1865
paper on the structure of aromatic
compounds. This paper is on Rod
Beavon's chemistry site. (Link to
further information on Kekule.)
• Joseph Achille Le Bel: tetrahedral
geometry of carbon (1874). This
paper is at the ChemTeam site as is
this photo.
• Jacobus van't Hoff: optical activity
and the tetrahedral geometry of
carbon (1874). This paper is at the
ChemTeam site. Link to a
biographical sketch of van't Hoff.
• A. D. Walsh, R. Robinson, C. A.
McDowell, and J.W. Linnett
separately discuss Walsh's proposed
description of bonding in
cyclopropane, 1947. These papers
are at Daniel Berger's Walsh
cyclopropane pages at Bluffton
College.
• Alexander Williamson: synthesis of
ether and structure of ethers and
alcohols (1850). Link to further
information about Williamson.
• Friedrich Wöhler: synthesis of urea
from inorganic materials,
conventionally regarded as fatal to
the idea that organic compounds
could only be produced through a
"vital force." This paper is at the
ChemTeam site, as is this picture.
• Charles-Adolphe Wurtz on amines
and their relation to ammonia (1849).
(Link to a photo of Wurtz or a
biographical paragraph.)

Periodic table and periodic law


• Humphry Davy: 1812 paper
searching for analogies among
elements.
• Johann Wolfgang Döbereiner: 1829
paper on triads of analogous
elements and their classification.
Link to a biographical sketch of
Döbereiner .
• Dmitrii Mendeleev, (1869): his first
published periodic table and the
abstract by which it was first known
in Western Europe. (Link to a
collection of on-line material about
Mendeleev.)
• Dmitrii Mendeleev, (1871): table
from Annalen, suppl. VIII, 133
(1871). This item is posted at Chris
Heilman's Pictorial Periodic Table
site.
• Dmitrii Mendeleev: excerpt from
1871 paper on periodicity of the
elements focuses on the properties of
the predicted element eka-boron,
now known as scandium. This paper
is on Rod Beavon's chemistry site.
• Dmitrii Mendeleev, (1889): Faraday
lecture on the Periodic Law, 20 years
after Mendeleev's first work on the
subject
• Julius Lothar Meyer, (1870). A table
of most of the known elements
arranged to show family
resemblances and a figure showing
atomic volumes varying periodically.
(Link to further information on
Meyer.)
• Julius Lothar Meyer: excerpt from
1870 paper on periodicity of the
elements. This paper is on Rod
Beavon's chemistry site.
• Henry Moseley (1913, 1914): X-ray
spectra of the elements reveal
integers characteristic of each
element, namely the atomic number.
This paper is at the ChemTeam site,
as is this picture and this essay on
Moseley and his work.
• J. A. R. Newlands, (1863, 1864,
1865, and 1866): his first attempts to
find relationships among the atomic
weights ("equivalents") of families of
elements and accounts of his "law of
octaves". The 1863 and 1864 papers
are a long way from the periodic
table, and even from his later law of
octaves (1865 and 1866 items). (Link
to a biographical sketch or view his
picture in the Edgar Fahs Smith
collection.)
• J. A. R. Newlands, On the discovery
of the periodic law: and on relations
among the atomic weights: 1884
monograph that collects all of
Newlands' papers on the subject
(This book is at Google Books).
• William Ramsay, (1897): expands
periodic table to make a new column
for noble gases; predicts discovery
and properties of neon. (Link to a
biographical sketch of Ramsay.)
• A. van den Broek: two letters on
numbering the elements (1911 and
1913). These papers are at the
ChemTeam site: 1 and 2.

Thermodynamics
• Francis Bacon (1620): Before caloric
and the kinetic theory, Bacon
reviewed a wide range of
observations about heat and related
phenomena to illustrate his inductive
scientific method, and suggested that
heat is related to motion. There is
even a mention of triboluminescent
candy (in Table II, number 11). (Link
to a biographical sketch of Bacon or
to a complete text of Novum
Organum.)
• Joseph Black: 1803 (posthumous)
paper on heat distinguished between
heat and temperature and described
specific heat and latent heat, even
though treating heat as matter.
• Sadi Carnot: Reflections on the
Motive Power of Fire (or "of heat" as
this translation has it), 1824. This
book is at the on-line Steam Engine
Library at the University of
Rochester. (Link to a biographical
sketch of Carnot.)
• Rudolf Clausius: excerpts from two
papers on entropy. The first (1850)
notes that heat is not indestructible,
and examines how it can be
converted to work with the flow of
heat from a warm body to a cold; the
second (1865) coins the term entropy
and states the second law of
thermodynamics. (Link to a
biographical sketch of Clausius.)
• Rudolf Clausius: 1857 paper on the
kinetic theory of gases; derives
expressions for the pressure of a gas
based from analysis of collisions for
average molecular speeds.
• John Dalton, excerpts from A New
System of Chemistry (1808).
Describes how heat (caloric) was
believed to combine with matter,
especially gases. (See also Lavoisier
excerpt in this section.) Heat capacity
of gases proposed to vary inversely
with atomic weight (like law of
Dulong & Petit).
• Humphry Davy: from Davy's first
scientific publication (1799), some
insightful ideas and dubious
experiments on the nature of heat and
friction. (Link to a biographical
sketch of Davy.)
• Daniel Gabriel Fahrenheit: 1724
paper observing several liquids to
boil at constant temperatures. (Link
to biographical information on
Fahrenheit.)
• Cato Guldberg and Peter Waage:
"Studier over Affiniteten", describing
law of mass action to the Norwegian
Academy of Sciences and Letters in
1864. This paper is at the ChemTeam
site, as is this picture.
• Josiah Willard Gibbs: preface to
Statistical Mechanics, published in
1902. This paper [pdf] is at the
American Institute of Physics
website. (Link to biographical
information on Gibbs.)
• John Herapath: excerpt of 1821
paper on kinetic theory of gases: heat
is motion, and there need not be
repulsive forces between gaseous
atoms. Link to biographical
information on Herapath.
• Germain Henri Hess: 1840 paper on
heats of reaction (Hess's law) This
paper is at the ChemTeam site. (Link
to a biographical sketch of Hess.)
• James Prescott Joule: 1845 note on
the relationship between heat and
mechanical energy (the mechanical
equivalent of heat). This paper is at
the ChemTeam site. (View Joule's
apparatus, or link to a biographical
sketch of Joule.)
• James Prescott Joule: 1851 estimate
of the speed of a gas molecule.
• Antoine Lavoisier: on caloric and its
role in the three states of matter,
from Elements of Chemistry (1789)
• Antoine Lavoisier: Oeuvres, (Paris,
1862-1893, 6 vols.): page images at
Panopticon Lavoisier includes
complete Traité élémentaire de
chimie
• Henri Louis le Chatelier (1884):
enunciates his principle concerning
chemical equilibrium. Link to a
biographical sketch of le Chatelier
• James Clerk Maxwell: introduces
Maxwell's "demon" and its
implications for the second law of
thermodynamics (1872).
• Julius Robert Mayer: on the
conservation or interconvertability of
energy (or force or vis viva, as the
paper says). Click here for a
biographical sketch of Mayer.
• Alexis-Thérèse Petit & Pierre-Louis
Dulong: complete 1819 paper on
heat capacities of elements, that
contains the law of Dulong & Petit.
(Link to biographical information on
Dulong and Petit.)
• Agnes Pockels: letter on surface
properties of water, sent to Lord
Rayleigh and later published in
Nature. This paper is at the
Contributions of 20th Century
Women to Physics site at UCLA.
(Link to biographical information on
Pockels.)
• François-Marie Raoult: 1882 paper
on freezing point depression. (Link
to biographical sketch of Raoult.)
• François-Marie Raoult: 1887 paper
on the lowering of vapor pressure.
• Benjamin Thomson (Count
Rumford): 1798 paper on the
quantity and nature of the heat
generated in boring a cannon. This
paper is at the ChemTeam site. (Link
to a biographical sketch of Rumford.)
• William Thomson (Baron Kelvin of
Largs): some thoughts (not all
correct--see Keith J. Laidler, The
World of Physical Chemistry, pp. 99-
100) on an absolute thermodynamic
scale of temperature (1848). (Link to
a biographical sketch of Kelvin.)
• William Thomson (Baron Kelvin of
Largs): 1852 formulation of the
second law of thermodynamics and
description of an absolute
temperature scale.
• William Thomson (Baron Kelvin of
Largs) (1865): an application of heat
transfer to geology, leading Thomson
to believe the earth is relatively
young.
• Jacobus van't Hoff: osmosis and the
analogy between solutions and gases
(1887). This paper is at the
ChemTeam site.

Others
• Justus Liebig: Familiar Letters on
Chemistry (1843). This monograph
on chemistry and some of its
applications to agriculture and
industry in the middle 19th century is
available courtesy of Peter Childs,
Limerick, Ireland.
• Philosophical Transactions of the
Royal Society, volumes 50-67 (1757-
77). This resource is available as
page images at the Internet Library
of Early Journals, Bodelian Library,
Oxford University. The entire
volumes are posted, so this resource
spans the range of natural
philosophy.
• Louis-Jacques Thenard: 1819 paper
announces discovery of hydrogen
peroxide and describes some of its
properties (including some painful
tests: don't try this at home)

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