Patented Dec. 1, 1953
'
2,661,360
UNITED STATES PATENT OFFICE
2,661,360
METHOD OF MAKING MERCURIC ACETATE
Frank P. Greenspan, Bu?alo, N. Y., assignor to
Buffalo Electro-Chemical Company, Inc., Tona
wanda, N. Y.
No Drawing. Application January 30, 1952,
l
_
‘Serial No. 269,133
6 Claims. (01. 260—431)
2
In an all-glass apparatus consisting of a two
neck ?ask equipped with re?ux condenser, to
prevent evaporation losses, and stirrer were
placed 24 g. of metallic mercury to which were
added 48 ml. of glacial acetic acid. The mercury
‘ This invention pertains to a method of making
mercuric acetate and more particularly to a
method of making it from metallic mercury.
Mercuric acetate is not only a useful compound
by itself, but is of considerable importance in
the manufacture of organic mercury compounds
such as the pharmaceutically valuable phenyl
mercury compounds.
was slurried up in the acid by means of the
stirrer and then there was added in one batch
18.8 g. of the above described peracetic acid solu
tion, this amount corresponding to a 10% ex—
Mercuric acetate has heretofore been made
by various methods, all involving the use of a 10 cess, calculated on a total active oxygen basis,
over the stoichiometric amount required. Agita
mercury compound as the starting material. In
tion of the reaction mixture was continued for
one widely used method, mercuric oxide is re
approximately 12 hours at room temperature,
acted with .glacial acetic acid. In another
after which time a copious amount of insoluble
method, mercuric chloride is digested with
sodium hydroxide in a sodium chloride solution, 15 mercurous acetate had formed.
the resulting mercuric oxide then being reacted
The ?ask with its contents was then heated on
a waterbath until the precipitated, insoluble
with glacial acetic acid. These as well as other
mercurous acetate was dissolved by transforma
methods, based on the use of a mercury com
pound as starting material, are relatively costly
tion into soluble mercuric acetate. There was no
and uneconomical. This is due to the fact that 20 trace of metallic mercury or other insoluble resi
metallic mercury is sold at substantially lower
due. The solution was then cooled to precipitate
prices than its compounds, such as the oxide,
the mercuric acetate, which was recovered by
?ltering off the liquid phase.
nitrate, chloride, etc.
The relative insolubility of metallic mercury
The product analyzed 61.7% Hg. It was readily
in acetic acid has prevented the use of the 25 soluble in water. Total weight of mercuric ace
cheaper metallic mercury in the manufacture of
tate recovered was 37.8 g., indicating a practi
mercuric acetate and although direct prepara
cally theoretical yield.
tion of the acetate from metallic mercury had
Example II
been recognized as the more desirable method,
In another test preparation of mercuric ace
actual practice has continued to make use of the
30 tate was carried out exactly as described in Ex
relatively expensive mercury compounds.
ample I, but very vigorous stirring was provided
I have now found that mercuric acetate may
for by using a high e?iciency stirrer. Agitation
be made in a highly ef?cient manner by treating
of the reaction mixture was continued for 2 hours
metallic mercury with peracetic acid in acetic
acid medium. While metallic mercury is prac 35 at room temperature. The ?ask with its contents
was then brought to re?ux temperature. After
tically insoluble in acetic acid, it will dissolve in
accordance with the present invention in per
acetic acid with the intermediate formation of
mercurous acetate, which is subsequently trans
formed into mercuric acetate by heating in pres 40
erice of peracetic acid.
“The following examples will serve to illustrate
the principle of my invention.
Example I
15 minutes of re?uxing, the precipitated, insolu
ble mercurous acetate had been completely dis
solved by transformation into the soluble mer
curic acetate. There was no trace of metallic
mercury or other insoluble residue. The solu
tion was then cooled to precipitate the mercuric
acetate, which was recovered by ?ltering off the
liquid phase.
45
The product obtained analyzed 61.4% Hg. It
was readily soluble in water. Total weight of
mercuric acetate recovered was 37.6 g., indicat
acting 90% hydrogen peroxide with glacial ace
ing a practically theoretical yield.
tic acid, the two reactants being used in a mole
Although intensive stirring will permit a sub
ratio of 1: 1.5 in the manner described by Green
span in J. Am. Chem. Soc. 68, 907, using nitric 50 stantial reduction in reaction time, as shown by
Examples 1 and 2, a similar increase in rate of re
acid as catalyst instead of the sulfuric acid cata
action may be obtained by working at tempera~
lyst described in that paper. The nitric acid
tures above room temperature, preferably again
was employed in an amount corresponding to
with intensive stirring as employed in Example 2.
1% of total volume of reactants. The resulting
peracetic acid 40% solution was then used in the 55 These variations in procedure are pointed out
here as obvious possibilities of influencing the
preparation of mercuric acetate as follows.
A peracetic acid solution was prepared by re
2,661,360
sirable, insoluble by-products and are suitable for‘
progress of the reaction, without being claimed
to be critical, as my invention is based on the
use in my process of making mercuric acetate.»
discovery that metallic mercury will dissolve in
Although all these acidic catalysts will serve‘
equally well for the preparation of peracetic acid
5 solutions and for their subsequent use in making
peracetic acid.
From a commercial viewpoint the above pro
cedure "will 'llb'e iprerei-r'eq although the ‘reaction
will take place in aqueous solution 'but withiza
gthe‘ldnercuri'cracetate, -I 'gprefer vto use I nitric acid
for-'i'eelsoris of cost andi‘eady availability. How-'
sacri?ce in time.
ever, where Icy-product formation is not objec-v
‘tionable, sulfuric acid or any other catalyst suit-‘
Furthermore, the procedure
may be varied by ?rst forming mercurous acetate
from metallic mercury anddsubstantially?the
stoichiometric amount of ‘peracét'ic acid. "The
- 1.0
,ablefor use in preparing peracetic acid may be
used.
white crystals of mercurous acetate "may :be
changed to soluble mercuric‘acetatebyl'heating’lin
‘ifaléturepf‘mer'curi'c acetate in practically theo~
an acid medium in presence of an oxidizing agent,
as which peracetic acid may serve. A slow trans- ‘
‘It, llfic mercury‘ and peracetic acid at a cost of
formation only Will take place'at ro'ofnftez?
_‘ _":ox'ff?atély"2/3"of the cost of manufacturing
‘ Thez'pro'cessi oi‘mycinvention permits the manu@
reticaly'iel'dsfbymeans of a reaction between me
mercuric acetate by any of the methods known
perature.
To insure high yields of uncontaminatedm'eb
I V, ‘
tb'ftliel'ai't involving the use of a mercury com
pound.
curic acetate, the reaction system employed
should“ be ‘free of 6 components apt" to "form .m'er 20 ’What Iclaim is:
Jcury ‘compounds “other 5 than ' the : desired "acetate.
lMo're" particularly, iorm‘ation T of = mercury room
pounds insoluble‘ in ' the‘ reacti'on"medium~’sho?ld
‘be'lavoided.
.
.
.
.
Y
.
The 40% pera'cetic acidisolu‘tion' of "commerce-is
7ordinarily‘prepared by reacting highly concen
11. The *method of making mercuric acetate
which‘ comprises reacting metallic mercury'with
tperacetic acid.
2. 'The method effmaking mercuric acetate
f'which'comprises reacting metallic mercury with
in presence ‘ofiminor?amounts vof ‘sulfuric acid,
‘Ip‘eracetic acid in "substantially stoichiometric
amounts.
:‘3. The method :of making mercuric acetate
‘which serves ‘to catalyze ‘the reaction.
"which comprises'reacting metallic mercury ‘in
trated hydrogen ' peroxide with‘ glacial‘l‘a'cetic‘ acid
A-"de
'scription of this ‘method “of "manufacturerhas 30-“aceticacid with ‘peracetic acid in substantially
been given by Greenspan in‘ J. Am.1Chem.‘1So.c.
.'6_8,]907. Although the i'am‘ount of sulfuric‘: acid
vvpresent in the end. product is small, peracetic
"which comprises‘ reacting metallic'mercury‘ with
acid solutions prepared'by'this method will con
an amount‘ I of‘ pera'c'etic acid sufficient-‘to - trans
~~tain approximately 1% by ‘volume ‘of sulfuric
acid. "If such pe'raceticia'cid 'solutionsare'used in
Tmy'me'thOd "of making mercuric ‘acetate; ‘the ‘sul
form vthe ? mercury to‘ ‘mercurous acetate then re
'1 'a‘ctingthe ‘latter'with 'peracetic' acid to form
~mercuric acetate.
stoiéhio'r'n‘etric ‘amounts
‘4. ~The-‘method of"?'making;:mercuric acetate
"furic acid pres'entwouldi‘give rise'to theforma
'_5.vThe method of ‘making mercuric ‘acetate
tion of a‘fsmall but ‘corresponding "amountwf "which ‘comprises "reacting ‘metallic mercury "with
vundesirable; insoluble‘ mercuridsulfate“ whiclrc'an 40""p'erac'etic°acid=inithe presence'of acetic ‘acid.
16. The method of‘imaking mercuric acetate
"be ?ltered off if‘ desired.
_ For this reason, the’sulfuricacidjcommoiily
"used as'the catalyst in T'the"preparation of"'per
acetic“ acid "solutions, ‘is’: preferably Ire‘pla‘ced‘ ” by
an" acidic‘g'c'at'alys?'not g‘i'vi'ngrise to'the‘iorina
tion of undesirable, insoluble'i'byéproductsiwhen
making mercuric'acetate in‘ accordance with the
which comprises intimately’agitating perac‘etic
“acid/with metallic‘ m'e'rcuryin thepreserice of
'_acetic acid'iuntil‘mercurous ‘acetate ‘is formed
45 ""then I heating {the ‘reaction ' mixture still ' contain
: ing peracetic?acidi to" speed i the " conversion-mer
‘ carats-acetate to mercuric a‘c‘etate.
‘process of my invention. ‘Of the various acidic
"catalystsiiisable inT'préparing peracetic‘acid‘s'olu
PIGRL‘EEN’SPAN.
‘ 'ti‘or'is, ‘nitric: acid? hydrogen "?uoride; bo : ' _ '?uo
References citea‘in ‘the ?le of this 'patent
wridefi‘?uob'oric 1a d,‘ ethane vl'sulfonic facidyép
_ ftolii'ene' ‘sulfonic' acid" and'camphorfsulf'onic fa'cid
‘among others“ will‘ ncvcause formation‘? or unde
. i’i’salk'owskiz “ Cheniiker-‘Zeitunc, ' vol. 40, pages
"448-449 (I916).