GUEST AUTHORS
Ralph Daniels, Clyde C. Rush,
‘ond Ludwig Bauer
University of Hlinois
Chicago 12
The we of the Felling and Benedict
tests for dotecting aliphatic aldehydes is recommended
by all writers of textbooks! and laboratory mantials in
organic chemistry. These tests employ a solution of
copper(II) ion in alkaline medium. To keep the test
solution homogeneous, the eoneenteation of eopper(I1)
ion is held low, through complex formation with tar-
trate ion in the Fehling test solution and with citrate
ion in the Benedict test. ‘The tests proper involve the
addition of a substance to the test solution and heating
the reaction mixture to 100°C.
According to the standard textbooks, aldehydes are
oxidized to the corresponding earboxylie acids with re-
duction of the copper(II) ion to copper(I) oxide,
appears asa yellow to red precipitate. When subjected
to the same treatment, ketones are not supposed to re-
duce copper(II) ion ‘and the test solutions retain
their blue color. Therefore, these test
if the texts are interpreted literally, aro presumed to
difezentiate between aldehydes and ketones
‘This simple interpretation for the test. reactions is not
in accord with experimental facts. While the test reae-
tions are positive for aldoses and reducing sugars, we
have fomd that extrapolation to simple aliphatic ale
dehydes is unwarranted. Exploratory experiments in
Suggestions of material suitable for this column and guest columns
fuitable for publiestion directly. are eagerly solicited. ‘Th
honld be sent with ne many detaile as possible, and particularly
‘with references to moner textbooks, to Kaeol 7 Mysels, Depart
ment of Chemistry, University of Southern California, Los
Angeles 7, Caloris.
“Sinee the purpose of thie column is to prevent tho spread ancl
continntion of errors and not the evaluation af individual texts
the source of errors discussed will ot he eited. ‘Tho error must
‘occur in atleast two independent standard books to be presented.
The standard conditions employed in our laboratory involve
‘eating the reaeon mixture for theee minutes in bailing water
bath. Further experimental details will be reported Fully shen
this study fs completa
Textbook Errors, 24
The Fehling and Benedict Tests
‘our laboratory have shown that under standard condi-
tions® the changes observed in treating a substance with
the test reagents fall into three eategories:
(1) A colorless: aqueous solution admixed with a
yellow to red precipitate results. The precipitate is
Cu.0; its formation represents @ positive test.
(2) Complex changes occur, with formation of a red
or dark-brown, gummy precipitate. Tn this ease, the
supernatant liquid may be blue, green, brown, yellow,
or orange. Nevertheless, this constitutes a negative
test because experiments in our laboratory indieate that
the precipitate isnot copper(I) oxide. Apparently these
changes have been mistaken for a positive test.
(3). The blue solution of the test reagent remains,
with or without the presence of a colorless immiscible
onganie layer. This is negative test.
‘We subjected several aldehydes and ketones to these
tests and found that carbonyl compounds eould be
classified aecording to the color changes deseribed above
Category (1): ghicose and the reducing sugars, achydrosyadip=
aldehyrle, glyoxal and pyruvic aldehyde,
Category (2): acetaldehyie,erotonaldel
‘and aldo
‘Category (3): benzaldchyde and aromatic aldehydes in general,
isobutyraldehyde, 2-ethyl-hexanol, and acetone,
A tentative conclusion can be drawn from these pre~
liminary experiments: Copper(ID) ion in Febling or
Benedict test. solution will be reduced to copper()
oxide by achydroxyaldehydes, e-hydroxy ketones and.
‘o-ketoaldehydes. Other aldehydes and ketones do not
produce copper(I) oxide. We have found that the Tol-
Tens’ test reagent. (an aqueous solution of diammine
silver(I) hydroxide) is infallible for distinguishing al
dehydes from ketones
le, cinnamaldehye,
It iv noteworthy that the Fehling test solution gives rite to
iw extensive changes than does the Benedict test solution. Tn
the caeo of the Fehling test, « tee of eopper (1) oxide may bo
fommod if an exees of test compound is employed.
Volume 37, Number 4, April 1960 | 205