JOURNAL OF CHEMICAL RESEARCH 2011 4(2) DECEMBER, 675–677 RESEARCH

PAPER 675

The mechanism of the reaction of the Tollens reagent

William E. Benet, Gabriella S. Lewis, Louise Z. Yang and D. E. Peter Hughes*
Westminster School, 17 Dean’s Yard, London SW1P 3PB, UK

The Tollens test for aldehydes has been used for over 100 years but no reason has been given for adding sodium hydroxide
to the silver nitrate before the solution is cleared with ammonia. In this paper, a mechanism is proposed which explains why
the addition of alkali makes the test much more sensitive.

Keywords: Tollens reagent, aldehyde, gem diol, free radical

very weak acids and at pH <10 they would be essentially
unionised. However, at higher pH ionisation would occur, that
Bernhard Tollens1 introduced his silver test for aldehydes for chloral being most pronounced as it is the strongest acid
when he was working on carbohydrates in the late ninteenth (pKa 10.0)4 because of the electron-withdrawing effect of the
century. This test involves the reduction of ammoniacal silver chlorine atoms. On the basis of this evidence it is likely that
nitrate by an aldehyde to give a silver mirror. If a few drops of
the second step in the reaction is as follows.
sodium hydroxide are initially added to the silver nitrate, the
test becomes much more sensitive though no explanation has
been given for this. There are two possible reasons. The higher RCH(OH)2 + OH− → R(CHOH)O− + H2O (2)
pH could increase the yield of the reaction and/or it could Oxidation of an aldehyde to an acid involves the transfer of
increase the rate of reaction. two electrons and must need two Ag+ ions, via a free radical.
A possible mechanism for these two electron transfers is as
follows.
Results and discussion
The overall reaction may be written as follows. R(CHOH)O− + Ag+ → R(CHOH)OAg (3)
RCHO + 2Ag(NH3)2 +
+3OH− → RCO2− + 2 Ag + 2H2O + 4NH3 R(CHOH)OAg → R(HCOH)O• + Ag(0) (4)
If the reaction is reversible, an increase in pH would increase the R(CHOH)O• + Ag(NH3)2+ → RCO2H + NH4+
yield. This suggestion was tested by setting up two electro- + NH3 + Ag(0) (5)
chemical cells. The first cell was a Ag/Ag(NH3)2+ half-cell against
a Ag/AgCl half-cell and the second a glucose/sodium gluconate RCO2H + OH− → RCO2− + H2O (6)
half cell against a Ag/AgCl chloride half cell. The addition of In equation (3) the Ag+ ion may be either hydrated or in the
sodium hydroxide changed the emfs of these cells only to a very form of the ammine.
small degree. Their values suggest that, in the absence of side A study of the kinetics of the reaction was carried out in
reactions, the reaction would go to completion. The fact that the order to test the proposed mechanism. The first set of results
Tollens test is more sensitive when the pH is increased and when was to establish the rate of the reaction with respect to the
the temperature is raised can only be explained by looking at the concentration of the aldehyde. The rate of the reaction was
individual steps of the reaction. These kinetic factors will be found using a colorimeter to measure the turbidity produced
considered next. by the precipitated silver. A solution containing 0.025 mol
A mechanism has been proposed for the reaction of ammo- dm−3 of Ag(NH3)2+ at pH 10.5 was prepared. A 2.0 cm3
niacal silver nitrate with several aldehydes.2 The authors did not sample of this solution was placed in a cuvette and the
record the pH at which they conducted their experiments but it can colorimeter was zeroed at 520 nm. A measured sample of 0.10
never have been >10 as they did not add any sodium hydroxide to mol dm−3 chloral was injected, the solution mixed and the
the mixture. Under these conditions, they found that the rate did times for absorbance readings of 0.1, 0.2, 0.3 etc. recorded.
not change when the pH was varied. They sug-gested that reaction The results gave a reasonable straight line whose slope was a
took place by the following mechanism. measure of the rate of the reaction, Fig. 1.
A calibration graph was set up for absorbance against silver
RCHO + H2O → RCH(OH)2 (1) concentration so that the rates could be expressed with units
+ •
RCH(OH)2 + Ag → RC (OH)2 + H + Ag(0) + mol dm−3 s−1, Fig. 2. It was found that silver at a concentration
•
of 0.00042 mol dm−3 in a 1.0 cm cuvette gave one unit of
RC (OH)2 + Ag+ → RC(OH)2+ + Ag(0) → RCO2H + H+ absorbance. All experiments were carried out at room
While this mechanism may be operating at pH <10, it does not temperature which was 20 ± 1 °C.
explain why the reaction goes much faster if the pH>10. The concentration of chloral was varied and it was shown
that rate was directly proportional to the chloral concentration,
It is known that some aldehydes (for example methanal and Fig. 3.
chloral) very quickly give a positive reaction with Tollens reagent A similar set of experiments was carried out, keeping the
at room temperature. Ethanal (and the higher alde-hydes) react concentration of the chloral constant and varying the concen-
much more slowly. Chloral and methanal rapidly hydrate to give tration of the Ag(NH3)2+. The concentration of the Ag(NH3)2+
gem diols3 and it seems likely that the initial hydration, as was always in an excess (≥1.0 × 10−3 mol dm−3), larger than
proposed by Prasad et al.2 is an essential first step. This hydration that of the chloral (5.0 × 10−4 mol dm−3). Under these condi-
is a reversible reaction whose position of equilibrium varies with tions, when the concentration of Ag(NH3)2+ was varied, there
the aldehyde under investigation. The equation shows that the was no significant change in rate, Table 1.
position of equilibrium is unaffected by alkali. Alkali does, It was not possible to measure the rate at very low concen-
however, act as a catalyst and equilib-rium is established very trations of Ag(NH3)2+ because the amount of silver precipitated
rapidly at

established so rapidly that equation (1) cannot have a signifi-

cant effect on the rate of the overall reaction, even with less
reactive aldehydes such as propanal. All gem diols behave as
676 JOURNAL OF CHEMICAL RESEARCH 2011

Table 1 Rate against silver concentration

Rate/mmol dm−3 s−1 0.03 0.03 0.04 0.04
[Ag(NH3)2+]/mol dm−3 0.001 0.01 0.05 0.1

would reduce the amount of free aldehyde available for reac-tion

with the ammoniacal silver nitrate and would make the test less
sensitive. A similar reduction might also take place if too high a
concentration of alkali was used. Under strongly alkaline
conditions, aldehydes may undergo two reactions, the aldol
reaction and the Cannizzaro reaction. These reactions take place
fairly slowly and it was unlikely that they caused a significant
reduction in the amount of free aldehyde present during the time
that the Tollens test was carried out. In order to minimise these
side reactions, it was necessary to prepare Tollens reagent with
Fig. 1 Typical absorbance against time graph for chloral with care, making sure that the ammonia was not in an excess and that
Ag(NH3)2+. the pH was not excessively high.
Because the reaction involved single electron transfers, it
must be a free radical reaction. A free radical mechanism can
be confirmed by adding a small sample of TEMPO which,
being itself a free radical, slows down the reaction.5 This was
found to be the case because the addition of TEMPO slowed
the reaction down by a factor of five.
If the proposed mechanism is correct, then at low pH, the
rate should decrease because the equilibrium for the ionisation
of the gem diol, equation (2), would lie to the left. With chloral,
whose gem diol has a pKa 10.0,4 the rate should decrease
below pH 11, while for ethanal (pKa 13.0), the rate should
increase only above pH 13. Such changes in rate were
observed as shown in Table 2.
Finally Tollens reagent was tried out on a variety of
different aldehydes. The results, Table 3, correlate with the
ease of formation of the gem diol of the aldehyde.
The time for the test to be positive (solution going grey) was
recorded as follows : < 5 s very rapid; 5–10 s rapid; > 1 minute
Fig. 2 Calibration of absorbance against [Ag(NH3)2 +]/mol dm−3.
slow; >5 minutes very slow. The warmed solutions were placed
in a water bath at 80 °C. Benzaldehyde, salicylaldehyde and
sucrose gave negative results at pH 10.5 but they gave a slight
positive reaction at pH 13 when the solution was warmed.
The difficulty in getting a positive response with benzalde-
hyde explains why there has been disagreement as to whether
it gives a positive reaction to the Tollens test or not. 6,7 The
slow positive reaction with sucrose was presumably due to
hydrolysis when the solution was warmed.

Table 2 Changes in rate with pH for chloral and ethanal

Choral pH 7.9 11 11.6 11.8
Rate/ mmol dm−3 s−1 0.003 0.003 0.02 0.03
Ethanal pH 12.8 13.0 13.2 13.3
Rate/mmol dm−3 s−1 0.0005 0.0005 0.003 0.003

Fig. 3 Rate against [chloral]/mol dm−3. Table 3 Qualitative results for Tollens’ reagent with different
aldehydes at pH 10.5
Aldehyde Observation
was too small for the absorption to be measured. Thus, because Methanal Very rapid at room temperature
the Ag(NH3) concentration was always in excess, the rate was Chloral Very rapid at room temperature
limited only by the concentration of the chloral (pseudo first order Ethanal Rapid at room temperature
Propanal Rapid at room temperature
conditions). Because the rate was unaffected when the Ag(NH3)2+ 4-Nitrobenzaldehyde Slow when warmed
was increased, it is likely that equation (4) and not equation (5) 2,4-Dinitrobenzaldehyde Rapid when warmed
was the rate determining step. Benzaldehyde Nil
When making Tollens reagent, care must be taken not to have Salicylaldehyde Nil
excess ammonia which makes the test much less sensi-tive. It is Glucose Slow at room temperature
known that ammonia readily reacts with aldehydes to give a Fructose Slow at room temperature
variety of addition products. These addition reactions Sucrose Nil
 JOURNAL OF CHEMICAL RESEARCH 2011 677

Conclusion to become grey. If, after several minutes, there was no obvious reac-
The addition of alkali makes the Tollens test much more sensi- tion at room temperature, the experiment was repeated with the tube
tive because the rate is much faster. The key feature seems to in a water bath at 80 °C. Because the higher aldehydes are sparingly
be the formation of the anion of the gem diol. The ease of for- soluble in water, they were initially dissolved in a 50/50 by volume
propanone/water mixture.
mation of this anion varies with the aldehyde and correlates
well with how rapidly they respond to Tollens test.
CAUTION: Sodium hydroxide solution must be handled with care,
especially at high pH. Tollens reagent was not kept for longer than
Experimental an hour as it may deposit explosive side products.
All chemicals were supplied by Aldrich and used without further puri-
fication. Tollens reagent of the required concentration and pH was made
up immediately before use. Typically 0.5 cm3 of 1.0 mol dm−3 NaOH was Received 22 October 2011; accepted 2 November 2011
added 20 cm3 of 0.050 mol dm−3 AgNO3. The mixture was stirred Paper 1100833 doi: 10.3184/174751911X13206824040536
magnetically and 1.0 mol dm−3 ammonia slowly added until a faint Published online: 27 December 2011
precipitate remained. The solution was then filtered and the filtrate made
up to 40 cm3. This typically produced 0.025 mol dm−3 Ag(NH3)2+ at pH References
10.5. A 2.0 cm3 sample of this solution was put in a 1.0 cm plastic cuvette 1 B. Tollens, Landwirt. versuchs-station., 1887, 29, 392.
which was placed in a Sherwood 260 colori-meter fitted with a 520 nm 2 T.V. Prasad, B.S. Ram and T. Rao, Curr. Sci., 1982, 51, 749.
filter. The colorimeter was zeroed with this solution. A measured volume 3 R.P. Bell, Advances in physical chemistry Academic Press, New York,
of 0.1 mol dm−3 of chloral or ethanol was injected from a syringe, the 1966, Vol. 4, p. 8.
mixture shaken and times recorded for absorbance readings of 0.1, 0.2, 0.3, 4 R.P. Bell, Advances in physical chemistry Academic Press, New York,
etc. The pH was measured at the end of the run. For the qualitative tests 1966, Vol. 4, p. 16.
on aldehydes, a solution of Ag(NH 3)2+ was made up with the above 5 www.en.wikipedia.org/Radical_(chemistry).
specifications. To approxi-mately 2 cm3 of this solution, enough aldehyde 6 F.G. Mann and B.C. Saunders, Practical organic chemistry, Longmans,
was added to make its concentration ≈0.1 mol dm−3. The time was London, 1960, p. 409.
7 www.ask.com/questions-about/Tollens-Reagent-with-benzaldehyde.
recorded for the solution