CARBOXYLIC ACID DERIVATIVES

A. Salts :

Introduction.

arboxylic acid salts, RCOO
-
M
+
, are ionic compounds which are
readily obtained from carboxylic acids by the latters reaction with
reactive metals or with metal oxides, hydroxides, carbonates and
hydrogen carbonates. The salts are soluble in water, unless of course, the alkyl chain is
so large that solubility is again substantially reduced. As seen earlier, the planar
carboxylate ion is stabilized by resonance.

Salts having a bulky or long-chained alkyl group are soaps and have the important
property of showing some compatibility both with polar/aqueous systems, where the
hydrophilic (water-loving) ionic -COO
-
side is involved, as well as with
non-polar/organic systems, where the oleophilic (oil-loving) or hydrophobic (water-
hating) alkyl group participates.
[Soaps fall out of favour where hard water, containing dissolved Ca
2+
ions, is being
used as the calcium salts, (RCOO)
2
Ca, are insoluble in water and give the disagreeable
scum. Detergents, often sulphonate salts, R-SO
3
-
M
+
, are used instead since the
calcium salts of these compounds are water-soluble.]


Nomenclature

alts of carboxylic acids, are derivatives of the carboxylic acids and
are therefore named accordingly i.e. the metal ions are first to be
mentioned, followed by the name of the parent carboxylic acid which
has the ending of oic acid changed to oate to indicate the replacement of the acidic
hydrogen(s). Thus salts of the methanoic acid are called methanoates, those of
ethanoic acid are ethanoates etc. :

C
S
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(As usual, substituent positions are given, where relevant, starting the numbering with
the carboxylic group carbon as this generally takes precedence in these compounds- an
example of this is given above showing the methyl substituents in blue.)

Note : Compounds having a name ending with oate do not necessarily have to be
ionic. Indeed, esters are similarly named but their bonding is by no means ionic. They
do have however an alkyl group instead of an acidic hydrogen.



Preparations

i) D irect reaction of reactive metals with carboxylic acids.

Reactive metals such as group I and II metals react with carboxylic acids to give salts
and hydrogen gas; the more reactive the metal the more vigorous the reaction and
hence it would be inadvisable to react carboxylic acids directly with potassium!


NB. Evolution of Hydrogen with a metal such as magnesium is often used as a test
for the presence of a free carboxylic acid (-COOH) group



ii) Reactions with metal oxides, hydroxides, carbonates and hydrogen
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carbonates
The mixing together of a carboxylic acid with metal oxides, hydroxides, carbonates or
hydrogen carbonates will give a replacement of the acidic hydrogens with the metal
ions:




Chemical Properties

(a) H ydrolyses of carboxylic acid salts.
As these salts are formed from weak acids, their conjugate bases are strong (defining an
equilibrium that lies in favour of the molecular carboxylic acid species).

A solution of these species in water is bound to give an overall removal of hydrogen
ions from the surrounding water, leaving a surplus of hydroxide ions resulting in
alkaline solutions.

or simply :

Release of free carboxylic acid : A more permanent hydrolysis reaction of salts would
come about by the addition of mineral acids (such as sulphuric or hydrochloric acids) as
the high level of surrounding H
+
ions is so high that a much higher percentage of the
carboxylate anions now become protonated to give the molecular carboxylic acid. This
process is important when one wants to convert a salt to its corresponding acid. (The
non-volatile sulphuric acid is often the better acid to consider but care will have to be
taken when the carboxylate in question is sensitive to the oxidising and dehydrating
actions of this aggressive acid. Methanoates can only be treated in this way if the acid
is kept cold and fairly dilute) :
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(b) D ecarboxylation Reactions
i) E lectrolytic : The previously encountered Kolbe reaction was seen to give an
electrolytic decarboxylation reaction where the carboxylate anion, after diffusing to the
attracting anode, releases an electron (its charge) and undergoes a decarboxylation to
generate a highly reactive (therefore short-lived) radical. As a considerable number of
these reactions are occurring simultaneously in close proximity to each other, it is not
unexpected to get two such radicals combining together to give an alkane.


ii) S odalime reaction : Also previously mentioned, the sodalime decarboxylation
reaction involves strongly heating the solid carboxylate salt with sodalime. In this
reaction the alkane is a carbon short on that of the parent carboxylate.

iii) T hermal decomposition of C alciumsalts : Heating calcium methanoates by
themselves produces calcium carbonate (which may also decompose to CaO and CO
2
if
the heating is strong enough) and methanal.(Cf. Aldehydes and Ketones). Other
calcium carboxylate salts give ketones if heated alone but will also give aldehydes,
amongst other things, if heated with calcium methanoate.



iv) D ecarboxylation via silver salts
Addition of bromine liquid to a silver carboxylate salt brings about a decarboxylation
reaction and produces a haloalkane (bromoalkane) as the organic product.


(c) A mide formation fromammoniumsalts
The heating of ammonium salts generally results in the, often temporary, separation of
the basic ammonia from the parent acid which recombine at a cooler part of the
apparatus in a process of sublimation (where the material goes straight to the gaseous
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state from a solid state missing out the liquid phase). The equilibrium leading to NH
3
and RCOOH formation is suppressed if free carboxylic acid is present and heating such
a mixture then gives the dehydration of the ammonium salt to produce the amide and
water.


(d) E ster formation by heating with haloalkanes
Carboxylic acid salts can conceivably react with haloalkanes to give a metal halide (- a
stable salt!) and an ester. Such a reaction can be carried out to give some desired ester :


(e) A nhydride formation by heating with acid chlorides
In a reaction, which is akin to that given for ester formation above, carboxylate salts
can be made to react with acid chlorides (and other acid halides) to give acid
anhydrides and an inorganic salt.



Tests and identifications

a. Metal ion (Cation)
Detection of metal ions is either by flame tests or by coloured/precipitation inorganic
reactions. For ammonium salts release of NH
3
gas with dil. aqueous NaOH is observed.

b. Carboxylic acid derivative (Anion)
i) Reaction with concentrated sulphuric acid
Methanoate and ethanedioate salts react with conc. H
2
SO
4
to give a dehydration
reaction resulting in the emission of CO from the former and a mixture of CO and CO
2
from the latter. All other salts will simply release the free carboxylic acid with H
2
SO
4

ii) Reaction with neutral FeCl
3
Reactions with neutral FeCl
3
can be useful in identifying some of the carboxylate
groups on the basis of the colour and behaviour of the carboxylate anion with the Fe
3+
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ion.
For methanoic and ethanoic acids (only) Fe
3+
gives a red/brown solution which, on
boiling precipitates out a brown basic salt. With benzoates, PhCOO
-
, a buff precipitate
is seen while reaction with ethanedioates gives a faint yellow colouration, which is a
stronger colour if a-hydroxycarboxylate salts are present.

iii) Reaction with Manganate(VII), MnO
4
-
Methanoates and ethanedioates will decolorise acidified potassium permanganate
solutions as they are oxidized to CO
2

iv) Reaction with Tollen`s reagent
Methanoates are the only carboxylate salts to give a silver mirror with Tollens reagent,
Ag(NH
3
)
2
+
(but they are not strong enough as reducing agents to bring about the
formation of Cu
2
O in Fehling`s though)












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