IMBSIR 83-2778

Discovery of Heavy Hydrogen and

Heavy Water

u s. DEPARTMENT OF COMMERCE

National Bureau of Standards

Office of the Director of Administration

Library Division

Washington, DC 20234

October 1983

Internal Report

Prepared for: U S. DEPARTMENT OF COMMERCE

ional Bureau of Standards

rary Division

shington, DC 20234

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NBSIR 83-2778

DISCOVERY OF HEAVY HYDROGEN AND

HEAVY WATER

Charles P. Saylor

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U S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Office of the Director of Administration

Library Division

Washington, DC 20234

October 1983

Internal Report

Prepared for: U.S. DEPARTMENT OF COMMERCE

National Bureau of Standards

Library Division

Washington, DC 20234

U.S. DEPARTMENT OF COMMERCE, Malcolm Baldrige, Secretary

NATIONAL BUREAU OF STANDARDS, Ernest Ambler, Director
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Note

The following brief account was prepared at ray request by Dr. C. P. Saylor

some years prior to his death in April 1982. It has been carefully

reviewed by several present and former staff members, including former NBS

scientist, Dr. F. G. Brickwedde, who participated with Dr. Harold C. Urey

and others in the experiments and events described by Saylor. In his

review Dr. Brickwedde, now Evans Pugh Research Professor of Physics emeritus at Pennsylvania State University, stated that "Dr. Saylor's paper

covers an important part of the history of the discovery of deuterium that

is not so well known ... and contains information important for the

chemical historian. I hope you will have it published."

Walter W. Weinstein

Historical Information Specialist

Library Division

1
Discovery of Heavy Hydrogen and Heavy Water

In any single chemical element the atoms are exactly alike. Almost!

They have the same charges, the same configurations, the same magnetic and

electrical properties. They react in the same way chemically. But about

three quarters of the natural elements have two or more kinds of atoms that

differ slightly in weight. They are co-mingled, usually in fairly constant

proportion. These atoms, differing only in mass, are known as isotopes

(meaning that they belong in the same place on the periodic chart). The

isotopes were long believed to be absolutely inseparable, although Keesom

and van Dyk had presented credible evidence of some separation of neon

isotopes by fractional distillation. Experimental evidence (later proved

invalid) was strong that hydrogen, the lightest element, had no isotope.

In 1931, however, two groups of scientists independently came to the

conclusion that hydrogen might have an isotope of mass number 2.

Vigorously and imaginatively they set to work. Before 1931 was ended both

groups had achieved a partial separation of the "inseparable" constituents.

They had established the existence of the heavy isotope of hydrogen. This

was later named deuterium. In both cases the separations were performed at

the National Bureau of Standards by bureau personnel, with NBS equipment.

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Harold C. Urey, who was then associate professor of chemistry at

Columbia University initiated one of these projects. He decided that the

most direct way of hunting a heavy isotope of hydrogen would be by distillation of the liquified element. In very few places in the world were they

able to liquify hydrogen, let alone subject it to fractional distillation.

Professor Urey hunted up a former Johns Hopkins University colleague,

Ferdinand G. Brickwedde. Brickwedde was then chief of the Low Temperature

Section of NBS. He liquified a large quantity of hydrogen and subjected it

to partial reflux distillation. He delivered the "tails" to Columbia.

G. M. Murphy, who was then a graduate student, together with Urey examined

the spectrum of the higher boiling fraction and found that faint lines

close to the normal lines of hydrogen were greatly enhanced. Their wavelengths differed from those of the normal Balmer series of ordinary

hydrogen by the amount calculated for hydrogen of mass 2. It was heavy

hydrogen. Urey, Brickwedde, and Murphy prepared an announcement of their

discovery in Physical Review . It was sent to the journal on December 5,

1931, and published in the first number in the new year.

Sometime between February 2, 1931, and the first signs of spring in

Washington, the time (early April) when the first leaves appear on the

willow trees, the other group began its work. Edward W. Washburn, chief

chemist of the National Bureau of Standards, concluded that the theoretical

evidence against the existence of a heavy isotope of hydrogen was faulty.

He thought of many ways of attempting an enrichment and tried a significant

portion of them. We only know of a few of them. He and his son sawed off

the top of a willow tree in his backyard. Such garrotted trees can add

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tons of new growth in a single year. He and his associates, E. R. Smith

and Mikkel Frandsen, measured the density of the residual water close to

the roots of the rapidly growing plant. The same was done with Jerusalem

artichokes. The water from the leaves and twigs of young willow shoots,

water from the Dead Sea, far from the Jordan River, and borax that represented the last drying up of inland salt lakes were tried. The water in

all of these shows higher density by a few parts in a million than normal

water. Ocean water has slightly more of the heavy isotope than terrestrial

surface waters.

He considered the end products from the electrolysis of water and with

Urey, in the spring of 1932, published a paper dealing with this and fractional distillation of water. With Smith he found that water absorbed by

active charcoal had more of the heavy isotope. The important experiments,

however, were those that used electrolysis.

When 98% of the water in a system is converted to gaseous elements,

the residual water, after purification, has a density increased by 600

parts in a million. They were not absolutely certain, however, whether

the increase in density was due to heavy hydrogen or to an increase of

the known heavy isotope of oxygen. They redesigned the electrolysis

vessels so that the released hydrogen and oxygen at all stages could be

combined in many ways and each with "normal" hydrogen or oxygen. This

lead to the astounding discovery by E. R. Smith that commercial oxygen

18 was significantly enriched with respect to 0 . Ordinary liquid air

is allowed to boil. The nitrogen evaporates carrying with it some of

4
the 0^^. That which remains is "heavy” by approximately 20 parts per

million. This was the first known separation of isotopes by an industrial

process. Power was turned on, probably in the new device, on December 9,

1931. There is some uncertainty whether the date refers to redesigned

apparatus or the original one.

While it isn't clear which team first acquired evidence of a heavy

isotope, there can be no doubt that the Urey, Brickwedde, and Murphy team

was much farther along in December of 1931. They first acquired indisputable data to prove the existence of H^. They submitted their note

first and published an authentic manuscript v^en the electrolytic experiments were in early stages. As happened, however, the method of separation

used by Washburn, Smith, and Frandsen turned out to be more important.

When our country went to work to develop a hydrogen bomb, the deuterium

(heavy hydrogen) was made by the electrolytic method. When during World

War II, the Germans endeavored to use heavy water as a neutron moderator

for the production of an atomic bomb, they set up great electrolytic

systems near the coast of Norway. We use it in the moderators of reactors.

When we begin to get a major part of our industrial energy from nuclear

fusion, it will probably utilize deuterium as a direct consequence of these

discoveries

.

Despite these dramatic applications, it can reasonably be argued that

the most important consequences of the discovery of heavy hydrogen and

heavy water have been the effects on research in the natural sciences.

These have involved the physics of the nucleus and the atom, the entire

5
question of isotope separation, synthesis of labeled organic compounds for

studying biological processes, investigation of disease metabolisms, and

other instances far too numerous to be detailed.

While the Urey team and the Washburn team began work in full

independence early in 1931, before the year was ended they knew of each

other's activities. Even a friendly rivalry developed. The joint paper by

Washburn and Urey probably grew from these associations. Urey received the

Nobel Prize in chemistry in 1934 for the discovery of heavy hydrogen and,

in the same year, Washburn (posthumously) received the Hillebrand prize in

chemistry for his work on heavy water.

6
significant References

W. H. Keesom and H. van Dyk, Proceedings of the Royal Academy of Amsterdam

42 (1931).

H. van Dyk, Physica, 203 (1931).

H. C. Urey, F. G. Brickwedde, and G. M. Murphy, Phys. Rev., 164

(1932).

H. C. Urey, F. G. Brickwedde, and G. M. Murphy, Phys. Rev., 1 (1932).

E. W. Washburn and H. C. Urey, Proc. Nat. Acad. Sci., 496 (1932).

E. W. Washburn, E. R. Smith, and Mikkel Frandsen, J. Chem. Phys., 2.» 288

(1933).

E. W. Washburn and E. R. Smith, J. Chem. Phys., J. > ^26 (1933),

E. W. Washburn, E. R. Smith, and Mikkel Frandsen, J. Research, Nat. Bur.

Stds. , J^, 453 (1933).

E. W. Washburn and E. R. Smith, J. Research, Nat. Bur. Stds., J_2, 305

(1934).

Edgar R. Smith, J. Chem. Phys., 298 (1934).

E. W. Washburn, E. R. Smith, and F. A. Smith, J. Research, Nat. Bur. Stds.

13, 599 (1934).
Ntt.lUA iwiv. i.ioi U.l. DIPT. OF COMM, 1. PUBLICATION OR 2. Porfermlng Organ. Report No,

BIBLIOGRAPHIC DATA

REPORT NO. 342 SHEET (See Instructions) NBSIR 83-2778

4. TITLE AND SUBTITLE

i. F^ubllcitlen Dit«

Octobtr 1963

Dlscovary of Htavy Hydrogan and Haavy Watar

5. AUTHOR(S)

Dr. C. P. Saylor

1. PERFORMING ORGANIZATION (If Joint or other than N8S. soa Instructions) 7. Contract/Grant No. NATIONAL BUREAU OF STANDARDS

DEPARTMENT OF COMMERCE 1. Type of Report & Period Covered

WASHINGTON, D.C. 20294

NBSIR

9. SPONSORING ORGANIZATION NAME AND COMPLETE ADDRESS (Street, City, State, ZIP)

National Bureau of Standards

Library Division

Washington, D.C. 20234

10. SUPPLEMENTARY NOTES

Vignette on the discovery of heavy hydrogen and heavy water, by Dr. Charles F.

Saylor prior to his death In 1982. Reviewed technically by Dr. C. Elsenhart,

Mr. W. R. Tilley, and Dr. F. G. Brlckwedde

DocuiTTnt d»icrlb«i compuff program; SP«I85, FIPS Softwf Summary, It atfeh«d.

11. ABSTRACT (A 200’Word or laii factual summary o^moit significant Information. If documtnt Includes a significant

bibliography or literature survey, mention It here)

Eleven significant references are listed at the end of the article.

The role of Dr. H. C. Urey, F. G. Brlckwedde, G. W. Murphy,

E. W. Washburn, E. R. Smith, and M. Frandsen In the discovery

of heavy hydrogen and heavy water.

12.

KEY WORDS (Six to twelve entries; alphabetical order; capitalize only proper names; and separate key words by semicolons)

Discovery of heavy hydrogen and heavy water; F. G. Brlckwedde; M. Frandsen;

H. G. Urey; G. M. Murphy; E. R. Smith; E. W. Washburn.

13.

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