The Chymists
are a strange class of mortals impelled by an almost insane impulse to
seek their pleasure among smoke and vapor, soot and flame, poisons and
poverty; yet among these evils I seem to live so sweetly that may I die
if I would change places with the Persian King.

Johann Becher (1635-1682)

 

During a recent
course of instruction in the Microscopical Identification of White-Powder
Unknowns, a question asked was, “How can you tell the difference between
sucrose and dextrose?”  Another was, “How can you determine whether an alum is
the potassium alum, the sodium alum, or the ammonium alum?”  Questions such as
these constantly come up during any microscopical identification course:  “Is
there a quick way to tell if aspirin is present in this analgesic?”  “Is boron
present in this sample of dentifrice?”  “Does the paper-coating consist of
cooked starch?”  Microscopists trained in classical methods realize that all of
these questions can be answered quickly and economically through the use of
simple microchemical tests which have been developed over the last 180 years:
elaborate and costly instrumentation is not necessary, even though such
equipment may be available.  Knowledge of these microchemical tests may be
obtained from numerous reference books, and acquisition of such references
should be an on-going process for the laboratory or for one’s personal professional
library.

 

In this article
I would like to survey the books that contain information on the performance
of microchemical tests, including spot testing; illustrations and/or annotations
are offered for each reference.  The presentation will be more or less
chronological so that the history of the entire branch of this microscopical
science will be apparent.  We will start with some definitions, and set
boundaries.

 

 

DEFINITION OF CLASSICAL MICROCHEMISTRY

 

In 1975, the American Chemical Society initiated a project
to prepare a history of the Society and of the various branches of chemistry,
to be published in the Society’s centennial year, 1976.  At the same time, the
executive committee of the Division of Analytical Chemistry decided that in
addition to supplying information for such a volume, it would undertake a
centennial history of its own, and thus A
History of Analytical Chemistry

[Laitinen, H.A. and G.W. Ewing (1977)] was produced.  The history
of the development of microchemistry and microanalysis as a special branch of
analytical chemistry for this book was prepared by Herbert K. Alber, who
studied under the founders of microanalytical chemistry at the Technical
University of Graz, Austria.  One of these founders was Fritz Pregl
(1860-1930), who was awarded the Nobel Prize in Chemistry in 1923.  Alber
defines the "Classical Period of Microanalysis" as the years 1900 to
about 1945, and states (p. 26) "It is generally agreed that Friedrich Emich
(1860-1940) at the Technical University in Graz, Austria, was the founder of
classical microchemistry."  He defines the years prior to 1900 as
"The Early Microchemical Period."  In this period, he states (p. 25)
that François-Vincent Raspail (1794-1878) "established himself as the
founder of chemical microscopy, and he probably can be recognized as the first
microchemist."

 

In the Preface to the first edition of his Elementary
Chemical Microscopy,
É.M.
Chamot (1915) stated, "…the earliest comprehensive work dealing with
microchemical methods was from the pen of an American—Theodore G. Wormley—whose
classic, The Microchemistry of Poisons, appeared
in 1867."  [Wormley (1867)]

 

Some historians attribute the first microchemical analysis
to Pliny (23-79 A.D.) who mentions an iron sulfate test in his 37-volume Historia Naturalis, the work in which he
described the entire natural world as far as it was known in his time, but it
is doubtful that the test was actually performed on very small samples, and a
microscope was certainly not in use.

 

As a microscopist and microchemist, I define classical
microchemistry as the period from the first application of chemical tests
conducted while actually viewing the results with a microscope, to the general
introduction of non-microscopical instrumental analysis.  For me that means from
Raspail’s earliest experiments (early 1820’s), through, say, the 1960’s – and
even to the present day, for those few practicing in the classical manner.

 

Spot tests, or spot-testing, is understood to mean color
and/or precipitate reactions resulting from mixing an unknown and a test
reagent in a “spot plate”.  Spot plates are small rectangular or square tiles
with ~1 cm diameter depressions in which the chemical reactions are conducted;
the spot plate may be made from white, blue, black, or black-and-white ceramic,
or from clear glass or plastic (which may be laid on paper of any color, for
contrast enhancement), and may have from one to twelve or more smooth concave depressions. 
A well-slide used in microscopy can be used for the same purpose.

 

“Chemical Microscopy” was defined by Émile Chamot in the
Introduction to his Elementary Chemical Microscopy as “the application
of the microscope to the solution of chemical problems”, for the purpose of
differentiating it from “microchemical” methods and tests.  He went on to
explain that “Microchemistry implies chemistry on a small scale,” and, indeed,
“all highly sensitive identification reactions and all quantitative methods,
which permit the use of samples smaller than are commonly necessary in
‘standard methods’”.  Under the term “chemical microscopy” Chamot included
“those methods, principles, and phenomena of chemistry which may be studied
particularly advantageously by means of the microscope….”

 

Microchemistry and spot tests are, therefore, vital methods
in the practice of chemical microscopy.

 

 

THE BEGINNINGS – 19TH CENTURY

 

FRANÇOIS-VINCENT RASPAIL

 

In 1814, the work of J. J. Colin (1784-1865) and H.F.
Gaultier de Claubry (1792-1878) showed that iodine colors starch blue. F.S.
Stromeyer (1776-1835) confirmed this test in 1815, but none of them thought to
apply the test microscopically. François-Vincent Raspail (Figure 1) applied the
iodine test for starches to sections of grasses, specifically for the
elucidation of the development of the embryo, and published a paper on his
findings in 1825.  For his microscope, Raspail had the optician Deleuil in Paris build for him a small simple microscope, a modified Cuff/Ellis type.  In the Spring
of 1826, he found new reagents that permitted the detection of sugar, oil, and
albumin within the cell.  Also, he developed microchemical tests for resin and
protein, all the while describing the colors and reactions.

 


Figure
1.
François-Vincent Raspail. From Dora B. Weiner’s Raspail;
Scientist and Reformer
(Columbia University Press, 1968).

Figure
2.
The term "chemical microscopy" used
by Raspail in an 1827 publication.

 

In 1827, he demonstrated the presence of silica in Spongilla, and
of calcium oxalate in the starch of monocotyledons, and published his results
[Raspail, François-Vincent (1827)].  In this publication he introduces
the term "chemical microscopy"
(Figure 2).  One of the two plates (Figure 3) in this publication
illustrates the silica and the calcium oxalate.  With these and numerous other
articles, Raspail founded both histochemistry and microchemistry.  His series
of articles culminated in the 1833 publication of his book (Figure 4), Nouveau
Systeme de Chimie Organique…
[Raspail,
François-Vincent (1833)]. which
is described in Duveen as the first work in which the microscope was
successfully employed in organic chemistry. In the first chapter he discusses
the theory, construction, and manipulation of the microscope, and illustrates
this in one of the twelve engraved plates (Figure 5).  One of the six
hand-colored plates (Figure 6) illustrates microchemical reaction products
and crystals found in botanical tissues.  In chapter after chapter he reports
the microscopical effects of employing various acids, bases, and salts to plant
and animal tissue.  On the basis of his chemical findings, he proposed a system
of classification based on physiological function, rather than morphology,
as Linnaeus had done.  An English translation of this book was published in
1834 [Raspail, François-Vincent (1834)].  What makes this book particularly
remarkable is the fact that it was written while Raspail was in prison. Raspail
was a political activist, and spent almost three years in prison, and wrote
as many books while confined. Dora B. Weiner has written an excellent biography
[Weiner, Dora B. (1968)] of Raspail, and Chapter 4 is of special interest,
because it was written in collaboration with Simone Raspail, François-Vincent’s
great-granddaughter, who, as a modern biologist and pharmacist, repeated some
of Raspail’s experiments with one of his own microscopes.

 


Figure
3.
Silica and calcium oxalate illustrated by Raspail in
1827.

Figure
4.
Title page of Raspail’s Nouveau
Systéme de Chimie Organique
(1833).

 


Figure
5.
Plate illustrating the theory and construction of the microscope,
from Raspail’s Nouveau Systéme de Chimie Organique (1833).

 


Figure
6.
One of six hand-colored plates from Raspail’s Nouveau
Systéme de Chimie Organique
(1833).

 

 

THEODORE G. WORMLEY

 

As already mentioned, in 1915 É.M. Chamot stated that
"…the earliest comprehensive work dealing with microchemical methods was
from the pen of an American –Theodore G. Wormley."

 

Theodore Wormley, M.D. (Figure 7) was Professor of Chemistry
and Toxicology in the Starling Medical College, and of Natural Sciences in
Capital University, Columbus, Ohio.  In 1857, he announced his intention to
publish a book on the microchemistry of poisons, and a prospectus announcing
its plan was published in March, 1861, at which time the drawings were almost
completed.  A
few years afterward (1865), A. Helwig published his Das Mikroskop in der
Toxikologie
[Helwig, A. (1865)], but
it would prove to be nowhere near the magnitude of Wormley’s book.  The first
edition of Wormley’s Micro-chemistry of Poisons [Wormley, Theodore G.,
M.D. (1867)], was
published in 1867.  In his Introduction, Wormley defines what he means by
microchemistry:  "By the term MICRO-CHEMISTRY
of POISONS, we understand the study of the chemical properties of
poisons as revealed by the aid of the microscope."  In the Preface, he
states, prophetically, "Heretofore the microscope has received but little
attention as an aid to chemical investigations, yet it is destined to very
greatly expand our knowledge in this department of study."  His superb
book is quite large (668 pages), and contains seventy-eight illustrations
engraved upon steel.  Interestingly, Wormley could not find an engraver who
would take on the task of engraving the microscopical images of the delicate
crystalline reactions, so his wife taught herself to engrave in steel, and
it was she who drew from nature and transferred to steel all of the microscopical
images in the form of thirteen beautiful plates.  Wormley affectionately
dedicated the book to her. In the back of the book, there is a long, fold-out
Tabular View of the Behavior of Alkaloids with Reagents. The described tests
and Wormley’s book in general, are as valid and useful today as they were almost
140 years ago. Demand for the book was strong, and necessitated a second
edition [Wormely, Theodore G., M.D. (1885)], in 1885, by which time Wormley
was Professor of Chemistry and Toxicology in the Medical Department of the
University of Pennsylvania. This second edition is enlarged to 784 pages, with
ninety-six illustrations, an Appendix on the Detection and Microscopic Discrimination
of Blood, and a chromolithographic frontispiece of blood spectra. Additional
tests and case-histories were added, as well as a revision of the chemical
nomenclature. Wormley’s book in either edition is
highly recommended, both for its historical significance and for its still
useful microchemical tests. It is found in both one and two-volume versions.

 

[Unfortunately, my copies are too
tightly bound to be scanned for illustrations without damage to the book.]

 


Figure
7.
Theodore G. Wormley, M.D. Portrait in McCrone Research
Institute Museum.

 

 

EMANUEL BORICKY

 

Emanuel Boricky was Professor Extraordinaire at the University of Prague, and Curator of the Bohemian Museum, in what is today the Czech Republic.  In 1877, he published a very important contribution on the microchemical
analysis of rocks and minerals.  The publication (Figure 8), Elements of a New Chemical Microscopical Analysis
of Minerals and Rocks
[Boricky, Emanual
(1877)], constituted a part of the Chemical-Petrological
Division’s Natural History Investigation of Bohemia.  In it, he described the
removal of small samples of the mineral components of rocks, and their
subsequent micro­chemical analysis with the aid of the microscope.  The
relatively short publication (80 pages) contains three woodcuts, and is also
illustrated with two lithographic plates showing the microscopical appearance
of the chemical reactions (Figure 9).  An English translation [Winchell N.H.
(1892)], of this valuable monograph was published by Professor N.H. Winchell in
the Nineteenth Annual Report (1890) of the Geological and Natural History
Survey of Minnesota (Minneapolis, 1892).

 

The practical microscopist will not
have a need for this publication, which, like Raspail’s works, are of
considerable interest, but they are essential items in the library of those
microscopists interested in the his­torical development of their craft.

 


Figure
8.
Title page of Emanuel Boricky’s monograph on Elements
of a New Chemical Microscopical Analysis of Minerals and Rocks
(1877).

Figure
9.
One of two lithographic plates illustrating microchemical
reactions, from Boricky’s 1877 monograph on the microchemical analysis
of minerals and rocks.

 

 

A. STRENG AND K. HAUSHOFER

 

A few years prior to the 1867 publication of Wormley’s
full-length book on the microchemistry of poisons, there had been several
individual articles on microscopical reaction products with poisons, and
several test reagents, as we know from Wormley’s Preface. It may be added that
after the death of Boricky, subsequent microchemical methods were devised by
Behrens, Streng, Haushofer, Rénard and Klément, and others.

 

Professor A. Streng of Giessen published several journal
and yearbook articles in the years 1883 through 1886 on the subject of
microchemical analysis of the more common minerals occurring in crystalline
rocks, just as Boricky had done, but Streng applied microchemical investigations
to compounds of some elements that had not previously been investigated in
this way, and he added several valuable reactions.  Moreover, he perfected the accessories and manipulations of
microchemical work.  For Streng, microchemical reactions were a valuable
auxiliary method to microscopical observations of ground and polished rock
sections, and to blowpipe analysis.  In addition to his journal/yearbook
articles of 1883-1886, Streng incorporated microchemical analysis in his book, Anleitung zum Bestimmung der Mineralien (Giessen, 1890).

 

K. Haushofer
went a step farther when, in 1885, he published his now “very rare” Mikroskopische
Reactionen
[Haushofer, K. (1885)], which was a
manual (Figure 10) for distinguishing the majority of the elements, but he
regarded the microscopical reactions (Figure 11) as supplementary to ordinary
qualitative analysis.  The importance of his work was the attempt to bring
all elements, even the rare ones, within the range of microscopical analysis.

 


Figure
10.
Title page of Haushofer’s very rare Mikroskopische
Reactionen
(1885).

Figure
11.
A page from Haushofer’s Mikroskopische
Reactionen
(1885), illustrating microchemical tests for mercury.

 

 

KLÉMENT AND RÉNARD

 

The treatise of Klément and Rénard, Reactions
Microchimiques; A Cristaux et Leur Application en Analyse Qualitative
[Klément,
C. and A. Rénard (1886)], published in 1886, is on a level with Haushofer’s
manual.  This work (Figure 12) abstracts all of the microchemical tests known
at that time.  It is also accompanied by numerous literary references, and a
table of 54 elements, with references to the text pages.  There are eight
engraved plates, each with twelve microchemical reactions illustrated.  The
illustrations are delicately engraved and each chemical reaction product is
shown in a full range of crystal habits and distortions (Figure 13).

 

Unfortunately,
the expectations suggested by the second part of the text title are not quite
satisfied.  As with Haushofer’s manual, the foundation of a microscopical
analysis is here, but when it comes to discriminating between closely allied
elements, such as cobalt and nickel, or zinc and cadmium, the tests leave much
to be desired.  Still, both works are closer to a complete microscopical
analysis.

 


Figure
12.
Title page of Klément and Rénard’s Reactions
Microchimiques; A Cristaux et Leur Application en Analyse Qualitative
(1886).

Figure
13.
One of eight engraved plates illustrating microchemical
reactions in Klément and Rénard’s Reactions
Microchimiques; A Cristaux et Leur Application en Analyse Qualitative
(1886).

 

 

H. BEHRENS

 

A serious source of error in all
microchemical methods is the fact that slight differences in the conditions
under which crystallization takes place may profoundly affect the form and
appearance of the crystals produced during a reaction: the acidity or
alkalinity needs to be controlled in a number of cases; the concentrations of
test substances and/or reagents may be important; and there are the cases in
which interfering ions must first be removed.  The microchemical tests published up to this point in
our survey were full of these problems.  Furthermore, there were still several
gaps in Klément and Rénard’s collection of reactions, and Professor Streng’s
manual did not have a means for detecting cadmium or nickel.

 

Professor H. Behrens (Figure 14) at the Hochschule in
Delft, Holland directed his efforts to removing the sources of error in the
published tests, and introducing many new and elegant methods. In addition
to rigorously testing all the older reactions and methods, he added the data
he obtained on the reliability and limits of applicability of the tests, as
well as appending his notes and cautions to his accounts of the various reactions.  He also added
tests for the rarer elements that were only then being found to be more widely
distributed in the earth’s crust than was formerly supposed.  Behrens wrote
articles on his microchemical methods in Dutch, German, and French.

 


Figure
14.
Professor H. Behrens. Portrait in McCrone Research Institute
Museum.

 

Professor John W. Judd, of the Royal College of Science,
London had been using microchemical methods for mineral identification in the
Geological Laboratories of that institution.  He learned of them when he met Boricky while
on a visit to Prague in 1875, two years before Boricky’s monograph appeared.  Later,
Professor H. Behrens decided to translate his own book on microchemical
analysis into English, and asked Professor Judd for his cooperation in bringing
out this new edition.  Thus far, there had been no books in English on this
subject except for Wormley’s treatise, which was devoted to poisons, and so
Professor Judd did not hesitate to accede.  And, thus, in 1894, we see the
publication in English of, A Manual of
Microchemical Analysis
[Behrens,
H. (1894)], to which Professor Judd contributed an Introduction.  This
is a very nice book to own – not absolutely necessary, because the tests will
be in Chamot and Mason, but from an historical perspective, you may enjoy
critical comments, such as (page 101), "Haushofer has tried to develop
staining of gelatinous silica with fuchsine… into a microchemical test.  It
is not of sufficient delicacy for this purpose; besides, the stain, recommended
by me for specimens of rocks, is of no use for gelatinous silica suspended
in a liquid."

 

Behrens ends the century with the 1899 publication of his Anleitung zur mikrochemischen Analyse, and
will open the new century with still another work.

 

Meanwhile, in America, a young man, Émile Monnin Chamot,
from Buffalo, New York, entered Cornell University in 1887, graduated with a
B.S. in 1891, and qualified for the Ph.D. in 1897.  His interests were in
toxicology and sanitary chemistry, and he had been introduced to the
application of microscopy to chemistry by Professor George Caldwell, the first
head of the Chemistry Department there.  As was customary at the time, Chamot
then went abroad for post-doctoral work.  He spent a year at the University of Nancy training in toxicology with Mace, and in Delft studying inorganic
qualitative analysis with Professor Behrens.  On his return to America, and
as the century closes, Chamot initiated a series of papers on microchemical
analysis that appeared in the Journal of
Applied Microscopy,
starting in 1899.

 

Before leaving the 19th century, it would be well to note
that there were very important, parallel developments going on, such as Otto
Lehmann’s introduction of hotstage methods, Michel-Lévy’s interference color
chart, advances in optical crystallography, and even other microchemical
methods in botany and physiology (urinary sediments, etc.).

 

 

TWENTIETH CENTURY

 

The new century starts out strong: Behrens publishes his Mikrochemische Technik [Behrens, H. (1900)], and Huysse’s beautiful
Atlas is produced.

 

 

A.C. HUYSSE

 

Huysse was a military pharmacist in the Royal Netherlands
Army.  1900 saw the publication of his Atlas
zum Gebrauche bei der mikrochemischen Analyse
[Huysse, A.C. (1900)] (Figure15).  It
was written for chemists, pharmacists, geologists and metallurgists, and for
university and technical school laboratories.  The beauty of this publication
lies in the 27 chromolithographed plates, each illustrating six microchemical
reactions (Figure 16); some are in black-and-white, but most are in color, even
down to the variegated green interference colors in yellow lead iodide (Plate
XIII).

A second edition [Huysse, A.C. (1932)], of this beautiful
Atlas (Figure 17) was published in 1932, with the chromolithographs (Figure 18)
now numbering 31.

 


Figure
15.
Title page of A.C. Huysse’s Atlas
zum Gebrauch bei der mikrochemischen Analyse
(1900).

Figure
16.
One of the 27 chromolithographed plates from A.C.
Huysse’s Atlas zum Gebrauch bei der
mikrochemischen Analyse
(1900).

 


Figure
17.
Cover title of A.C. Huysse’s Atlas
zum Gebrauche bei der mikrochemischen Analyse
(1932).

Figure
18.
One of the 31 chromolithographic plates illustrating
microchemical reactions, from A.C. Huysse’s Atlas
zum Gebrauche bei der mikrochemischen Analyse
(1932).

 

 

CARL G. HINRICHS

 

Gustavus Detlef Hinrichs was Professor of Chemistry in
the Medical Department of St. Louis University.  In the first couple of years
of the new century, he planned the publication of a work on microchemical analysis
which would not require the use of hydrogen sulfide.  He requested his son,
Carl Gustav, a chemistry instructor in the same medical department—in fact
the youngest instructor—to work out such a course.  The resulting book, First
Course in
Microchemical Analysis [Hinrichs, Carl Gustav (1904)],
was
published in 1904, simultaneously in St. Louis, Missouri; New York and
Leipzig; London; and in Paris.  It is a curious book.  The father wrote the
introduction to crystallographic chemistry.  There is a Crystal Atlas, with
plates of hand-drawn crystals, illustrations of microscopes and goniometers,
two portraits, and several graphs.  Then there is an Atlas of Micro-crystals,
carefully drawn, as they appeared in the field of a microscope; some are
hand-drawn, others are taken from works of other authors.  The plates occupy 64 pages.  The
father’s introduction (pages 65-100) is followed by
the son’s course (pages 101-145).

 

Probably
only those interested in the historical aspects of microchemistry will require
this book.

 

 

N. SCHOORL (UTRECHT)

 

Schoorl’s name comes up around the first
decade of the century.  He published a number of articles on microchemical
analysis in the years 1907-1909, which were collected together in book
form as Beiträge zur mikrochemischen Analyse [Schoorl, N. (1909)].

 

 

J. DONAU (1877-1960)

 

Dr. Julius F.
Donau’s Die Arbeitsmethoden der Mikrochemie….[Donau, Julius (1913)] was published in
1913.
 
This book (Figure 19) constituted Volume IX of a more
comprehensive Handbook der mikroskopischen Technik, published by the
editors of Mikrokosmos.  The first part of this slim book is
devoted to qualitative microchemistry, and the second part introduces
quantitative methods.

 


Figure
19.
Front cover of Julius Donau’s Die
Arbeitsmethoden der Mikrochemie
(1913).

 

 

FRIEDRICH EMICH (1860-1940)

 

In his rectoral address at the Technical University in Graz, Austria in 1899, Emich described his philosophy of
working with milligram amounts of material.  He started with qualitative
techniques for both inorganic and organic microanalysis.  He developed new
micro­crystal tests conducted on microscope slides, developed fiber tests for
nanogram amounts of acid, alkali, boron, and sulfide, and developed the
techniques for working in glass capillaries, not only for identification, but
for the preparation of organic compounds.

 

He improved techniques for working in
capillary cones, elementary tests for organic compounds, fractional
distillation, boiling point determination, and many other techniques which
today go under the name of his co-workers only. Emich’s main interest, however,
was in quantitative microanalysis.  His gravimetric procedures with milligram
amounts of material, using newly developed micro-balances, were shown to be
as reliable as macro-procedures. He is today recognized as the founder of
quantitative microanalysis—both inorganic and organic; however, the Nobel
Prize would be awarded to F. Pregl, who adopted Emich’s methods.

 

The first
edition of Emich’s Lehrbuch der Mikrochemie [Emich, F.
(1911)], was published by Bergmann in Wiesbaden in 1911.  The second
edition came out in 1926 [Emich, F. (1926)].  The first
edition of Emich’s Mikrochemisches Praktikum [Emich, F.
(1924)], was published in 1924, with a second edition in 1931 [Emich, F.
(1931)].

 

 

H. BEHRENS AND
P.D.C. KLEY

 

1915 was a memorable
year in microchemistry, because Behrens and Kley published their book on
organic qualitative microanalysis, and Chamot published the first book version
of his text on chemical microscopy.  Let us start by going back to before the
turn of the century, when young Émile Chamot first went to Delft and met
Behrens.  As it turned out, Behrens at the time was providing his new
assistant, P.D.C. Kley (Figure 20), with detailed instruction in inorganic
qualitative microscopical analysis, and Chamot was fortunate in being included
in the instruction.  On leaving Behrens, Chamot asked how he might repay the
valuable instruction, and was told by Behrens to start courses in this field in
America. Kley stayed on as Behrens’ assistant, and together they authored the
Organische mikrochemische Analyse [Behrens, H. and P.D.C. Kley (1915)], which was
published by Voss in Leipzig in 1915.  Several other
editions followed, the fourth edition appearing in 1921/1922. This fourth
edition was translated into English by Richard E. Stevens, and published in 1969 [Behrens, H. and
P.D.C. Kley (1969)].

 


Figure
20.
P.D.C. Kley, Prof. Behren’s assistant, at the microchemical
bench in Delft. Cropped section of portrait in McCrone Research Institute
Museum.

 

Also published
in 1915 was Kley’s Part 2 of Behrens-Kley Mikrochemische Analyse (Figure
21 and Figure 22), a series of Tables for the systematic determination of
minerals using microchemistry and physical constants [P.D.C. Kley (1915)].

 


Figure
21.
Cover of P.D.C. Kley’s Mikrochemische
Analyse
,
Part 2 (1915).

Figure
22.
Title page of P.D.C. Kley’s Tabellen
zum systematischen Bestimmung der Mineralien
(1915), Part
2 of Behrens-Kley Mikrochemische
Analyse
.

 

 

TUNMANN

 

In the tradition started by
Raspail almost 100 years earlier, Dr. O. Tunmann wrote a textbook in 1913
devoted to the application of microchemical tests to plant materials [Tunmann
(1913)].  This text (Figure 23) on plant microchemistry contained 137 illustrations
(Figure 24).  A second edition updating the text was published in 1922.

 

Figure
23.
Title page of Tunmann’s Pflanzenmikrochemie (1913).

Figure
24.
A page from Tunmann’s Pflanzenmikrochemie (1913).

 

 

MOLISCH

 

Also in the tradition
started by Raspail and complementing Tunmann’s books on plant microchemistry,
Hans Molisch published several books on plant structure and microchemistry,
including the third edition of his Mikrochemie der Pflanze (1923).  The
third edition of this text (Figure 25) contained 135 text figures, including
line drawings (Figure 26), and photomicrographs (Figure 27).

 


Figure
25.
Title page of Molisch’s Mikrochemie
der Pfanze
,
Third edition (1923).

Figure
26.
Line drawing of microchemical test from Molisch’s
Mikrochemie der Pfanze (1923).

 


Figure
27.
Photomicrograph of microchemical test from Molisch’s
Mikrochemie der Pfanze, Third edition (1923).

 

 

ÉMILE MONNIN
CHAMOT

 

Émile Monnin Chamot (Figure 28), true to his
promise to Professor Behrens, started teaching microchemical analysis
immediately upon his return to Cornell.  The first courses consisted of
informal lectures, demonstrations, and laboratory practices.  Students were
guided by their notes and by mimeographed and typewritten sheets.  Between 1899 and 1902, Chamot
wrote about twenty articles on microchemical analysis for the Journal of
Applied Microscopy.  
These articles, along with the laboratory direction
sheets and lecture notes, became the nucleus for Chamot’s book, Elementary
Chemical Microscopy
[Chamot É.M. (1915)], published by
Wiley in 1915.  Many copies of this first textbook for American
chemists bear the imprint year 1916, because within one year of its
appearance, a third thousand had to be printed. Incidentally, in spite of
Raspail’s introduction of the term "chemical microscopy," Chamot is
often credited with having coined the name in about 1914, because he
realized that in addition to microchemical analysis, there were physical and
physicochemical factors involved in chemical behavior, and then there were also
the quantitative methods of Emich and Pregl being developed; these all applied
to problems that chemists were called upon to investigate.  In his 1915 Preface,
Chamot acknowledges his indebtness to the then late Professor Behrens, and to
Simon Henry Gage, Professor Emeritus of Histology and Embryology, also at Cornell,
about whom Chamot says, "It is largely due to the spirit of optimism and
love for research with which this indefatigable investigator is ever surrounded
that the author was originally led to enter the field of applied microscopy
when first a student."

 


Figure
28.
Émile Monnin Chamot. Portrait in McCrone Research
Institute Museum.

 

 

America then entered
World War 1, and a partly rewritten and enlarged second edition [Chamot, É.M.
(1921)], of Chamot’s book came out in 1921.  In the Preface
to the second edition, Chamot notes how the microscope had come to be regarded
as a necessary adjunct to the chemical laboratory, and how it had been applied
to problem solving during the war in more new applications than in the
preceding quarter of a century.  Here he also announces that a Handbook
of Microscopic Qualitative Analysis
is in preparation, and that it will
include copious photomicrographic illustrations.  Finally, he states his
indebtedness to Simon Henry Gage, and to Clyde Walter Mason for helpful
suggestions.

 

 

É.M. CHAMOT AND
C. W. MASON

 

In 1930, volume 1 of the Handbook of
Chemical Microscopy
[Chamot, É.M. and C.W. Mason (1930)], by É M. Chamot
and C. W. Mason was published by Wiley, with the announcement that Volume 2 was in
preparation.  This first volume is devoted to the Principles and Use of
Microscopes and Accessories, and Physical Methods for the Study of Chemical
Problems.  Volume 2, on Chemical Methods and Inorganic Qualitative
Analysis, came out the following year, 1931.  Interestingly,
the authors
state in their Preface that "In spite of the continued growth which
microscopical qualitative analysis has undergone, it is noteworthy that the
methods of this branch of chemistry, as taught by Behrens in the early
nineties, stand with little need for modification…. Building better than he
knew, he chose reagents which are still unexcelled for convenience, rapidity,
and versatility."

 

After eight years of continued progress
in chemical microscopy, and classroom observation, a second edition of the Handbook [Chamot, É.M.
and C.W. Mason (1938 & 1940)], was deemed necessary.  Accordingly,
Volume 1 of the second edition was published in 1938, and Volume 2 in 1940.

 

Chamot retired in 1938, and died in 1950.  Mason prepared a
new (third) edition of Volume 1 only of the Handbook…. and Wiley
published it in 1958 [Chamot, É.M. and C.W. Mason (1958)]. There
is a Michel-Lévy chart in full color in this volume, and the footnote references
number in the thousands.

 

Volume 2 of the Handbook …. went out of
print in 1968, and was reprinted in 1989 by the McCrone
Research Institute (Chicago), but is again no longer available.

 

In the years
between 1940 and 1968, the Handbook…. was reprinted
a number of times, sometimes in a smaller format, and always on different paper;
variations in the paper are as common as in Winchell’s Elements of
Optical Mineralogy.
C.W. Mason again
revised Volume 1 only as a fourth edition in 1983 [Mason C.W.
(1983)]; Chamot’s name was dropped as co-author in this edition.  Mason has since
died.

 

Intriguingly, there exist notes prepared
by Chamot for a proposed Volume 3 on the Identification
of Organic Acids.
The practical
microscopist must have the second edition of Volume 2; the reprint is
fine. Of Volume 1, my preference is for the third edition [Chamot, É.M.
and C.W. Mason (1958)].

 

 

The 1920’s

 

The decade opened with the publication of Davy
and Farnham’s (1920) book on Microscopic Examination of the Ore Minerals
[(Davy and Farnham (1920)].  What is uncommon about this book (Figure 29), is
that it is thumb-indexed by microchemical reagent.  Here (Figure 30) is a page
from the Determinative Tables giving the reaction to HNO3, HCl,
KCN-N, and FeCl3.

 


Figure
29.
Title page of Davy and Farnham’s Microscopic
Examination of the Ore Minerals
(1920).

Figure
30.
A page from the Determinative Tables in Davy and Farnham’s
Microscopic Examination of the Ore Minerals (1920).

 

The 1920’s saw the reissue
of older books, such as the second edition of Chamot’s Elementary
Chemical Microscopy
[Chamot, É.M. (1921)], but there were
several new books of some interest. The first one that comes to mind is Some
Microchemical Tests for Alkaloids
[Stephenson, Charles H. (1921)], by
Stephenson and Parker.  At the back of this book are 26 plates, each
with six photomicrographs illustrating the microcrystal tests for the
alkaloids.  There is also a fold-out Table of Microchemical Reactions of 51
Alkaloids With 35 Reagents, which is still being used in current drug
identification courses.  Other useful features of this book include a Table
Showing Best Tests for Each Alkaloid, and a Scheme for 21 Identification of Alkaloids.

 

In 1922, Chamot reported on
microscopical researches involving problems with small arms ammunition primers
that were coincident with the entrance of the United States into World War
1. Small
arms ammunition, especially .30 caliber cartridges intended for field and
aircraft machine-guns, was characterized by a disturbingly high number of
misfires traceable to the primers.  Mercury fulminate had been used in some
compositions, and azides were being considered; the "souring" of
some primers was ultimately attributed to bromate contamination creating a
chemical reaction in potassium chlorate priming mixtures.  At any rate, Chamot
reported on his researches in a now scarce booklet, The
Microscopy of Small Arms Primers
[Chamot,
É.M. (1922)].

 

In 1923, Fritz Pregl (1860-1930),
who earned an M.D. degree at the University of Graz in 1894, was awarded the
Nobel Prize in Chemistry.  His work is traceable back to 1909, when he visited
Emich’s laboratory in Salzburg, and heard him lecture on micro methods.  This
inspired him to develop a variety of quantitative micro methods.

 

1923 was also the year that saw the publication of the
first edition (Figure 31) of Mayrhofer’s Mikrochemie der Arzneimittel und Gifte 
[Mayrhofer (1923)]; the
microchemical reactions are illustrated with line drawings (Figure 32).  Part 2
of this work on the microchemistry of pharmaceuticals and poisons (Figure 33)
was published in 1928.  Part 1 deals with the microchemistry of the “official”
inorganic and organic acids and their salts, and Part 2 is devoted to the
microchemical analysis (Figure 34) of organic pharmaceuticals.

 


Figure
31.
Title page of Mayrhofer’s Mikrochemie
der Arzneimittel und Gifte
(1923).

Figure
32.
Two of the 53 text figures in Mayrhofer’s Mikrochemie
der Arzneimittel und Gifte
(1923).

Figure
33.
Title page of Part 2 of Mayrhofer’s Mikrochemie
der Arzneimittel und Gifte
(1928).

Figure
34.
Photomicrographic illustration of microchemical reactions
in Part 2 of Mayrhofer’s Mikrochemie
der Arzneimittel und Gifte
(1928).

 

In 1921, the third edition of Kley’s earlier Behrens-Kley
Mikrochemische Analyse
was published [Kley, P.D.C. (1921)].  This edition
(Figure 35) contains 146 text figures, illustrating not only microchemical
reactions (Figure 36), but discussions on the optical investigation of mineral
grains (Figure 37), use of compensators (Figure 38), etc.

 


Figure
35.
Title page of the third edition of Kley’s Behrens-Kley
Mikrochemische Analyse
(1921).

Figure
36.
Microchemical reaction illustration from Kley’s
Behrens-Kley Mikrochemische Analyse (1921).

Figure
37.
Refractive index determination from Kley’s Behrens-Kley
Mikrochemische Analyse
(1921).

Figure
38.
Use of compensator from Kley’s Behrens-Kley
Mikrochemische Analyse
(1921).

 

In 1925, Heffer published a charming little book called, Practical Chemistry by Micro-Methods [Grey, Egerton C.(1925)], written
by Egerton C. Grey, Professor of Chemistry at the Government Medical School
in Cairo.  The frontispiece
(Figure 39) consists of a photograph of a Student Examining the Effect of
Mixing Two Drops.  Reference is made to a color plate (Figure 40), which shows
the reaction of eighteen different common metal ions using three different
reagents (ammonium carbonate, potassium iodide, and ammonium sulfide).  The
book was intended for schools or for the earlier part of a university course,
so as "to give the student a taste for this fascinating subject."

 


Figure
39.
Frontispiece from Grey’s Practical
Chemistry by Micro-Methods
(1925), showing "Student Examining the Effect of Mixing Two
Drops."

Figure
40.
Color plate showing reaction of 18 different metal
ions using three different reagents. From Grey’s Practical
Chemistry by Micro-Methods
(1925).

 

Joseph B. Niederl took courses with Emich and Pregl, and
then started teaching quantitative organic microanalysis at New York University in 1925.

 

The entire subject of quantitative
microanalysis requires a survey all of its own. Some highlights, however, must
include Pregl’s Quantitative Organic
Microanalysis
[Pregl, Fritz
(1924)], translated by Fyleman; the Julius Grant books (five editions) Quantitative Organic Microanalysis, Based on the
Methods of Fritz Pregl
[Grant
Julius (1924, 1930, 1951)], Niederl’s
text, Micromethods of Quantitative Organic
Elementary Analysis
[Niederl, J.B.
and V. Niederl (1938)], Paul
Kirk’s Quantitative Ultramicroanalysis [Kirk, Paul L. (1950)], and
Korenman’s Introduction to Quantitative Ultramicroanalysis [Korenman, I.M. (1965)].

 

 

ROSENTHALER

 

Dr. Leopold Rosenthaler,
Professor at the University of Bern, Switzerland, wrote several books of
interest to the microchemist during the 1920’s and 1930’s.  His Grundzüge
der chemischen P