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1901 2012
Prize category:
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The Nobel Prize in Chemistry 1925
Richard Zsigmondy
Award Ceremony Speech
Presentation Speech by Professor H.G. Söderbaum, Secretary of the Royal Swedish Academy of Sciences, on December 10, 1926*
Your Majesty, Your Royal Highnesses, Ladies
and Gentlemen.
Around the middle of the 19th century the English scientist
Graham put forward a new principle of subdividing matter by
classifying all substances into one of the two great classes:
crystalloids and colloids. A crystalloid, e.g. common salt, is
characterized in that it passes in the dissolved state readily
through membranes such as parchment paper or collodion films and
also that it exhibits a rapid free diffusion. A colloid, on the
other hand, e.g. glue, is unable to pass through such membranes
and diffuses extremely slowly, in contrast to the crystalloid. In
passing it may be mentioned that the name colloid originates
precisely from kolla, the Greek
word for glue. Other examples of colloids well known to everyone
are proteins, starch, rubber, water glass, etc.
It was very soon found that sometimes one and the same substance
can occur in one case as a crystalloid and in another case as a
colloid. For instance, gold with mercury produce a crystalloidal
solution, whilst gold in an aqueous solution exists only in the
colloidal state. It is consequently more correct to differentiate
between crystalloidal and colloidal states rather than
between crystalloidal and colloidal substances. When it
then became a question of forming an opinion of the reason for
these different states, several people, e.g. the American
scientist Lea, had recourse to the concept of allotropy which
existed previously in chemistry, and was illustrated by the
typical example of phosphorus with its two so-called allotropic
modifications, the yellow and the red. Others again imagined the
difference to be that the colloidal solutions were not uniform
throughout, not homogeneous as the crystalloidal ones, but that
they contained particles, molecule aggregates, of a size which
exceeded by many times the size of the molecules in a
crystalloidal solution. But which of the two interpretations was
the correct one?
This difficult problem was brought a decisive step nearer to its
solution by the invention of the ultramicroscope at the
beginning of the 20th century. The idea originated from Zsigmondy
and was developed in detail by him in cooperation with
Siedentopf, an able optician with the firm of Zeiss. The
principle of this instrument is briefly that the intensely
illuminated object, the solution to be examined, is observed by
means of a microscope from the side, i.e. vertically to the axis
of the incident light beam. In this way it is possible to
differentiate between particles of such small size that they
could not be observed under an ordinary microscope, just as the
dust particles suspended in the air in our rooms, which are
invisible under ordinary conditions, sometimes become visible
when the sun's rays shine through the window in a definite
direction in relation to the observer. With the ultramicroscope,
and especially the improved type which is called the immersion
ultramicroscope, progress has been such that particles with a
diameter of down to 8 mm are
recognized with arc-light illumination, and down to 4 mm when using the sun as the light source.
Zsigmondy now found that various gold colloids prepared by him
contained delimited particles under the ultramicroscope although
they had appeared completely homogeneous under an ordinary
microscope. He further showed by a systematic study of the gold
colloids that they can be produced in a varying distribution of
fineness, onwards from colloids the particles of which are
invisible even in the ultramicroscope, up to ones whose particles
lie at the limit of visibility in the microscope. He showed that
Lea's solutions of so-called allotropic silver are really built
up from small, ultramicroscopic silver particles. He finally
showed that the examination of other colloids also gave similar
results. This proved the correctness of the particle hypothesis,
and the heterogeneous nature of colloidal solutions was
established. It has also been possible to determine
quantitatively the size of the particles. The procedure is to
delimit optically a small volume of the colloid to be examined,
after which the number of particles in it is counted. If the mass
concentration of the colloid is known, it is easy to obtain the
mass of the particles, and from this - assuming, for example, a
spherical shape and normal specific gravity - the size can be
calculated.
As mentioned, there are colloids which are so fine-grained that
their particles cannot be distinguished even in the
ultramicroscope. However, Zsigmondy has made also these
accessible to scientific observation by the invention of the
so-called nucleus method. This was also first applied to
gold, the classical metal of colloid research, and it is carried
out by introducing the fine-grained gold colloid into a reducing
solution from which metallic gold is slowly precipitated. This
now settles on the invisible, colloidal gold particles so that
they - the so-called gold nuclei - gradually increase in size,
and finally become visible in the ultramicroscope. In this way
gold particles with a diameter of down to 1 1/2 mm have been measured, and it has become possible
to determine the particle size - thus, the degree of
heterogeneity - in the case of all gold colloids. It was possible
to apply the method later to a large number of other metals, and
it has proved to be of the greatest importance for a whole number
of investigations which had the object of establishing general
principles for colloids, indeed it may seem doubtful whether
these investigations could have been at all possible without
Zsigmondy's nucleus method.
It is a generally known fact that when a colloidal solution, for
example one of protein, is treated with certain substances such
as salts or acids - in short, electrolytes - it coagulates or
"solidifies to a jelly", i.e. it passes into a semi-solid form or
a so-called gel. Corresponding, although not completely similar,
conditions also arise in regard to colloidal metals, the reason
being that the primary particles join together to form large
aggregates, i.e. they increase in size whilst diminishing in
number.
Zsigmondy's work has quite simply been pioneering as regards the
explanation of the mechanism of the coagulation phenomenon and
also as regards the study of the structure of gels. It has been
found that coagulation progresses extremely slowly at a low
concentration of the electrolyte, whilst with increasing
concentration the rate of coagulation gradually increases up to a
certain stage - at the so-called threshold value - when it
rapidly reaches a limiting value which then no longer increases
further or changes when the concentration is further increased.
Within the rapid coagulation, as Zsigmondy found, the coagulation
time is independent not only of the concentration of the
electrolyte but also of its nature, whilst on the other hand, the
threshold value and the rate within the range of slow coagulation
are characteristic for each individual electrolyte.
Based on these facts, Zsigmondy expressed several important
fundamental ideas for explaining the coagulation mechanism which
were later formulated more accurately and developed to a
mathematical theory of coagulation by Smoluchowski. In turn,
Zsigmondy and his pupils have been able to verify experimentally
this theory in its various details whereby its great general
validity has been proved in a brilliant manner.
The brief review given here of some of the most important work of
Zsigmondy is necessarily highly incomplete, if not to say
fragmentary, but should surely suffice to show how it pioneered
the way and opened up new regions in a field of research which
had so far been difficult of access, a field which must be
recognized as having the very greatest importance for human
knowledge. Let us only remember in this connection that all
manifestations of organic life are finally bound to the colloidal
media of the protoplasm.
This by way of motivation for the decision of the Academy of
Sciences to award the Chemistry Nobel Prize for 1925 to Dr.
Richard Zsigmondy, Professor of Chemistry at the University of
Göttingen, for proving the heterogeneous nature of
colloidal solutions and for the methods used which have laid the
foundation of modern colloid chemistry.
Professor Zsigmondy. When the Royal Swedish
Academy of Sciences after mature consideration decided to award
you the Nobel Prize in Chemistry for the year 1925, it did this
in the firm conviction that it would only be making itself the
executor of the unanimous verdict of the entire scientific
world.
Convinced that the significance of your pioneering work which is
generally recognized today, will in future times stand possibly
in an even clearer light, the Academy allows itself to offer you
its sincere congratulations on the well-deserved reward the
external insignia of which you are now about to receive.
* The Nobel Prize in Chemistry 1925 was announced on November 11, 1926.
From Nobel Lectures, Chemistry 1922-1941, Elsevier Publishing Company, Amsterdam, 1966
Copyright © The Nobel Foundation 1925
MLA style: "Nobelprize.org". Nobelprize.org. 23 May 2013 http://www.nobelprize.org/nobel_prizes/chemistry/laureates/1925/press.html
