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The Mechanism of The Reaction of The Tollens Reagent
The Mechanism of The Reaction of The Tollens Reagent
PAPER 675
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.
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