The Early History of the

Thermocouple
By L. B. Hunt, M.SC., Ph.D.
Johnson Matthey & Co Limited

The name oJ Seebeck is indissolubly associated with the discovery of

thermoelectricity and the thermocouple. But how did Seebeck’s researches
jit into the general background of contemporary scientijic work, and how
did they lead on to the development of the modern thermocouple pyro-
meter? This article outlines the early history of the couple up to the time
when it became accepted as an accurate and reliable means of measu.ring
high temperatures.

At this distance from the events, and Among the small band of physicists who
looking back from our present understanding were active in this way was Thomas Johann
of the nature and applications of electricity, it Seebeck. Born at Reval in Estonia on April
is almost impossible to appreciate the excite- gth, 1770,the son of a wealthy merchant, he
ment and enthusiasm that prevailed in the left his native town at the age of 17 and took
little world of physics around the year 1820. up the study of medicine in Berlin. His strong
Until Volta announced the discovery of his inclination for natural science, together with
pile in 1800 physicists had had no means of his financial independence, caused him to
studying the effects of a steady current. This, change his plan, however, and he embarked on
and the voltaic cell which rapidly succeeded it, a career of private research, first in Bayreuth
provided for the first time a simple means of and later in Jena. Here he worked on optics
maintaining a continuous current, and led to a and on the nature of colour, but in 1810 he
burst of activity in the study of the chemical left Jena for Nuremberg, and it was here that
effects of electricity. Oersted spent some time as Seebeck‘s guest.
In 1818he accepted a position with the Berlin
Oersted and Ampbre Academy of Sciences, and moved to that city.
As this first wave of enthusiasm was perhaps
dying away, Oersted discovered that a current Seebeck’s Discovery
of electricity flowing in a wire lying parallel Here it was, of course, that he learned of
with, and close to, a magnetic needle had the Oersted’s discovery, and at once applied
power of deflecting the needle. This discovery himself to the study of electromagnetism; in
was announced in 1820, and it immediately December of the same year, 1820, he read a
set off a new wave of interest all over Europe, paper to the Academy dealing with the
this time in the mechanical effects of a current. magnetic influence of a current. Only a few
Arago, in the same year, produced the first months later, in August 1821, he announced
electromagnet, while Ampere, within a week to the Academy (I) his discovcry that two
of hearing of Oersted’s experiment, had different metals forming a closed circle, in the
shown that one electric current had a magnetic absence of moisture, showed magnetic pro-
influence upon another. No doubt was left perties when subjected to a difference of
that magnetism was essentially an electrical temperature at the point of contact. He had
phenomenon. experimented with a number of combinations

Platinum Metals Rev., 1964, 8, (l), 23-28 23

of metals (finding an antimony-bismuth At this time Ohm was working on the
combination the most effective), and had propagation of electricity through a conductor
ascertained the effects of both heating and and on the concept of resistance, but he was
cooling one of the junctions, He established having trouble in his experiments owing to the
that the deflection of the magnetic needle variations in the current obtained from his
arose from the difference in temperature of batteries. A suggestion was made to him by
the metallic junctions, that the effects varied Poggendorf that he should replace the
for different metals, and were greater for batteries by a thermo-electric circuit, and this
greater differences of temperature. I n his idea Ohm adopted in his classical research in
results he reported the movement of the 1826. He used a circuit of bismuth and
needle in terms of an easterly or a westerly copper, one junction being immersed in a
deflection, and he described the phenomenon steam jacket and the other in ice.
as ‘ctherm~-magneti~m”, taking objection in
later years to the expression “thermo- The First Measurement of
electricity”. High Temperature
Second in importance at the time only to The first recorded suggestion to make use of
Oersted’s experiment, Seebeck’s discovery Seebeck’s discovery as a means of measuring
also spread rapidly among European physi- high temperatures came from A. C . Becquerel
cists, and it was repeated in every centre of (2)in a paper read to the Academie Royal des
research. Sciences in Paris on March 13th, 1826. His
investigations included observations of the
Faraday and Ohm needle deflection obtained with a number of
Among others, Faraday carried out the combinations of metal wires when one junc-
experiment, and he records it in his diary as tion was heated in a spirit lamp, and he
follows: deduced that, for certain of these com-
Octr. 21, 1822 binations, the intensity of current developed
Dr. Seebeck’s Expt. A n . Phil. 2V.S. VoE. iv. was proportional to the rise in temperature.
p . 318
The most suitable combination, he decided,
Bar of Antimony and brass wire; the bur was a circuit consisting of platinum and
being heated at one end the north pole of a needle palladium wires.
would go round it as represented i n the lower
Jigure-the effect on the needle very decided,
Becquerel further showed that the charac-
powerful even and constant. teristics were independent of the diameter of
The dotted lines represent the state of the the wire, and also that an impure platinum
loire as ascertained from former experiments.
wire would give rise to a current if coupled
with a pure platinum wire; he pointed out, in
fact, the necessity for cleaning the platinum
in nitric acid to avoid spurious effects due to
contamination.

The Magnetic Pyrometer

In 1836 Professor C. S. M. Pouillet (3), of
Paris, also before the Academie Royal des
Sciences, put forward his “magnetic pyro-
meter” and detailed its construction. This
instrument, almost incredible by today’s
standards, comprised a platinum wire sealed
into the breech of a gun, the wire passing up
the barrel but prevented from touching the

Platinum Metals Rev., 1964, 8, (1) 24

sides by a filling of magnesia or asbestos. The
breech of the gun was then to be inserted
into the hot zone.
In the course of his long and classic
researches on heat Henri Regnault (4)made
use of Pouillet’s iron-platinum couple, but he
found such irregularities that he emphatically
condemned the whole idea of the thermo-
electric method. Regnault’s unhappy ex-
periences were due partly to his use of iron as
one element, and also to his failure to employ
a high-resistance galvanometer. Later, in
1862,Edmond Becquerel(5) took up the study
of his father’s platinum-palladium thermo-
couple and used it as an intermediary with an
air thermometer in determining the melting
points of a number of substances. As a result
of his researches he succeeded to some extent
in rehabilitating the reputation of the thermo-
couple, and he derived an expression-much
too complex-for the relationship between
temperature and electromotive force.
Henry Le Cliatelier
Thefather of the modern thermocouple, Le Chatelier
E.m.f. - Temperature Relationship was the $rst to employ a rhodium-platinum alloy
Avenarius ( 6 ) also investigated this rela- against platinum and to recommend calibration
in terms of the fired points of melting or boiling
tionship, working with the rather curious of pure substances
combinations of steel and nickel-silver, and
copper and zinc. He arrived at a parabolic first reference to the use of iridium-platinum
formula of the type: alloys in thermocouples.
E =a +bt +cte
The Work of Le Chatelier
but a few years later apparently realised his And so to 1885and Henry Le Chatelier (8),
error and withdrew his arguments. whose name, together with that of Seebeck,
In the meantime Professor P. G.Tait (7)of will always be associated with the thermo-
Edinburgh University had conducted a series electric pyrometer and with the use of a
of experiments in an attempt to construct rhodium-platinum alloy. Born in Paris in
“thermo-electric diagrams”, and concluded 1850, Le Chatelier studied chemistry under
that the electromotive force is in general a Sainte-Claire Deville, but in 1870 was called
parabolic function of the absolute tempera- into the army and took part in the siege of
ture, He also reported that a very small Paris. Subsequently he practised as a mining
amount of impurity, or even of permanent engineer, but in 1877 joined the French
strain, is capable of considerably altering the School of Mines to teach chemistry, becoming
line of a metal in the diagram. Professor of Industrial Chemistry some nine
Professor Tait used “platinum-iridium years later. Many years afterwards Le
alloys containing respectively 5 , 10 and 15 Chatelier recalled the origins of his work on
per cent of the latter metal. These were thermocouples in the following words:
prepared for me from pure metals by Messrs. “In 1885, when I attacked the problem of
Johnson and Matthey”. This constitutes the the measurement of high temperatures, it is

Platinum Metals Rev., 1964, 8, (1) 25

 fair to say there existed nothing definite organisation of the United States Geological
available on this important question; we Survey with the objective of studying the
possessed only qualitative observations for
temperatures above 500°C. Engaged at that physical constants of rocks. Barus was put in
time in industrial studies relative to the charge of this laboratory, which was located
manufacture of cement, I sought a method first in New Haven, Connecticut, but moved
which above all would be rapid and simple, and
decided on the use of thermo-electric couples, to Washington two years later. He realised
intending to determine the order of magnitude that few important steps in the study of this
of the sources of error noticed by Regnault. branch of geology could be made until
The readings of even a crude galvanometer
might be very useful in technical work, methods for the accurate measurement of high
provided the limitations of its accuracy were temperatures and pressures had not only been
appreciated. I soon recognised that the errors
perfected but rendered easily available, and he
attributed to this method could easily be
eliminated by discarding in the construction therefore undertook a most comprehensive
of the couples certain metals, such as iron, study of temperature measurement; this was
nickel, and palladium, which give rise to
singular anomalies. Among the different metals published as a memoir of some 300 pages in
and alloys studied, pure platinum and the alloy 1889. Numerous alloys of platinum were
of platinum and rhodium which are still used investigated as thermocouple elements, most
today, gave the most satisfactory results. . . .
I recommended also the calibration of the of them having additions of 2, 5 and 10 per
couples, not against the air thermometer cent of other elements, but he came to rest
directly, as Becquerel had tried to do, but in for general use on platinum against 20 per
terms of the fixed points of boiling or fusion of
certain pure substances, in such a way that, cent iridium-platinum. Barus was aware of
when these temperatures should be known the importance of purity and homogeneity in
more exactly, as is the case since my earlier
researches, the results could be corrected with
certainty.”
Le Chatelier devoted considerable time and
effort to the development of the thermocouple
pyrometer, and arranged for the instrument
to be manufactured by Carpentier, the suc-
cessor of the famous Ruhmkorff, at 20 Rue
Delambre, Paris. The reputation of these
instruments spread rapidly and widely. I n
1890, for instance, the great American
metallurgist, Professor H. M. Howe wrote (9):
“Thanks to the labors of M. Le Chatelier,
we have at last a pyrorneter capable of measur-
ing easily, accurately and rapidly extremely
high temperatures, indeed, those approaching
the melting point of platinum. And this is not
an apparatus which each must construct for
himself; it is for sale ready made. Indeed, it is
SO far simplified that it has actually entered
into practical use for the control of high
temperatures in steel works, glass works and
gas works.”

American Investigations
Sir William Roberts-Austen
Contemporary with Le Chatelier but quite
Chemist to the Royal Mint, Professor of Metallurgy
independently of him, Dr. Carl Barus (10) at the Royal School of Mines and Jirst investigator
was engaging himself actively in the measure- to the Alloys Research Committee of the Institution
ment of high temperatures. I n 1882 a new of Mechanical Engineers, Roberts-Austen was
quick to appreciate the usefulness of Le Chatelier’s
physical laboratory had been set up within the thermocouple pyrometer

Platinum Metals Rev., 1964, 8, (1) 26

his thermocouple materials, and he drew upon
the resources of the Bishop and Co. Platinum
Works at Malvern, Pa., for the preparation of
his materials. The couples were then cali-
brated at the boiling points of mercury, zinc
and certain organic substances.

Roberts-Austen’s Contribution
At this time the Institution of Mechanical
Engineers had established its Alloys Research
Committee, with the initial objective of study-
ing the effects of alloying elements on the
properties of metals, and had appointed W. C.
Roberts-Austen, who combined the posts of
Chemist to the Royal Mint and Professor of
Metallurgy at the Royal School of Mines, as
investigator. I n his first report (11) in 1890 to
the Institution, Professor (later Sir William)
Roberts-Austen said:
“In the present investigation it is necessary
to measure much higher temperatures; and
fortunately an accurate method is at hand. Edward Matthey
Early in 1889 I had occasion to employ the
pyrometer devised by M. H. Le Chatelier, and Investigated the homogeneity of rhodium-platinum
was satisfied as to its being extremely trust- alloys and conjirmed the $findings of Le ChateEier
worthy and convenient up to temperatures and Roberts-Austen as to their suitability for
over 10oo”C. or 18oo”Fahr. The instrument thermometric use
in fact enabled me to confirm the fundamental
observations of M. Osmond respecting the
critid points of iron and steel, and to dernon- “It is asserted that even long wires of the
strate the results in a lecture delivered before platinum-rhodium alloy are homogeneous,
the members of the British Association in and therefore do not give rise to subsidiary
September 1889.” currents which would disturb the effect of the
main current produccd by hcating the junction;
Since 1875 Roberts-Austen had interested but very careful experiments to determine
himself in the problems of liquation or whether this is the case have yet to be made.”
segregation of the constituents of alloys, and
This uncertainty aroused the interest of
had been most painstaking in his measurement
Edward Matthey, who carried out a lengthy
of temperatures using the laborious calori-
investigation (12) on the liquation of alloys of
metric methods then available. He therefore
the platinum metals. On the rhodium-
welcomed most readily the new type of
platinum alloys he had the following comment
instrument and proceeded to adapt it for the
to make:
production of autographic records of the
cooling and solidification of molten metals “Much attention has lately been drawn to an
and alloys. alloy of pure platinum, with 10 per cent of
rhodium, which has become important from
the excellent service it has rendered in the
Problems of Homogeneity determination of high temperatures. The alloy
of platinum with ID per cent of rhodium is
Some doubt still remained, however, con- used with pure platinum as a thermocouple,
cerning the absolute reliability of the rhodium- and it is, therefore, interesting to be able to
set at rest any doubt which might arise as to
platinum alloy, and Roberts-Austen referred
this alloy being uniform in composition when
to this: melted and drawn into wire.”

Platinum Metals Rev., 1964, 8, (1) 27

 Matthey prepared a melt of one and a half alloys of platinum and rhodium, lately pub-
lished in the ‘Philosophical Transactions’,
kilograms of 10 per cent rhodium-platinum, settled the question in favour of the rhodium-
which he cast into a sphere of two inches platinum thermo-junction, for I was satisfied
diameter. The sphere was then sectioned, and that the alloy of platinum with 10 per cent of
rhodium is as homogeneous as any known
samples were taken for analysis from a number alloy could well be, and is therefore admirably
of locations between the surface and the adapted for use as a thermo-junction, pure
centre. T h e maximum difference between the platinum being the opposing metal.”
centre and the outside was found to be 0.6 The instrument employed was obtained
per cent of platinum and 0.04 per cent of from Paris and was used in the full scale
rhodium. H e concluded: operation of the oxidation process in the
“This result proves that the alloy is not works of Johnson Matthey, being one of the
subject to liquation, and fully justifies the first such pyrometers to be used in industry.
high opinion that H. Le Chatelier and Roberts-
Austen have formed as to its suitability for T h e only earlier record of a Le Chatelier
thermometric measurements.” pyrometer being used in this country is that
At much the same time, 1892, Edward given by Sir Robert Hadfield (rq), who
Matthey was concerning himself with the purchased one from Carpentier in April 1890.
extraction and refining of bismuth and he This gave excellent service in the steel works
contributed a series of papers on this subject of Hadfields Ltd. in Sheffield until British-
to the Royal Society. An extract from one of made pyrometers became available just after
these papers (13)~dealing with the tempera- the turn of the century.
ture at which arsenic can be oxidised off from The first mention of thermocouples being
bismuth, reads as follows: available for temperature measurement in
“The work of Roberts-Austen has shown this country appears in a Cambridge
that a thermo-junction is practically the only Instrument Company catalogue of 1898, but
form of pyrometer that can be used for delicate
thermal investigations of rhis kind, but the the manufacture of them did not begin until
question arose which particular thermo- 1902, when special stocks of platinum and
junction should be adopted. Was it well to rhodium-platinum were procured from
use the platinum-iridium one as advocated by
Barus, or the platinum-rhodium one suggested Johnson Matthey and marketed in suitable
by H. Le Chatelier? My previous work on the porcelain tubes (15).

References
I T. J. Seebeck .. *. Abhandlurgen der physikalische Klasse dcr Komglichen Akudemie
d m Wissenschafrer ZU Berlin, 1822-23, pp. 265-373
2 A. C. Becquerel . . __ Ann. chim. phys., 1827, 31, pp. 371-392
3 c. s. A M . l’ouillet , . .. Compt. rend., 1836, 3, pp. 782-790
4 H. V. Regnault . . .. Relation des Experiences, Paris, 1847,I, p. 246
S E.Becquerel .. .. Compt. rend., 1862, 55, p. 826
6 Avenarius . . .. .. Pogg. Ann, 1863, 119,p. 406
1864, 122, p . 193
7 P. G. Tait . . .. .. Trans. Roy. SOC.Edin., 1872-73, 27, p. 125
8 1-1. Le Chatelier . . .. Compt. rend., 1886, 102, p. 819
J . de Phys., 1887, 6, p. 23
9 13. M. Howe .. .. ling. and Min. J., 189, 50, p. 426
I0 C. Barus . . .. .. 13~11.U.S. Geol. Surwey, 1889, h’o. 54
Phil. Mug., 1892, 34, p. 376
I1 W. C. Roberts-Austen .. 1st Rep. Alloys Hes. Comm., Inst. Mech. Big., 1891
I2 E. Matthey .. .. I’hiZ. Trans., 1892, 183, p. 629
I3 B. Matthey .. .. I’roc. Roy. Soc., 1893, 52, p. 467
14 Sir Robert Hadfield , . Trans. Fareday SOL.,1917-18, 13, p, 208
IS Anon .. .. .. Eyineeriqq, 1945, 159,iMay 11th and zgth, pp. 361 and 41

Platinum Metals Rev., 1964, 8, (1) 28