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Xerox University Microfilms
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LD3907
oG7 Seliksorn Bernard, 1922-
195° Purther phase studies of sulfamates
• S*+ in aqueous medium* New Yorkc 1950
13b typewritten loaves* diagrs*,
tables* 29cm*
Thesis (Ph°D.) - New York Univer
sity, Graduate School, 1950®
Bibliography: p*l33-i3o*
C57606
c
Shelf List
Xerox University Microfilms, Ann Arbor, Michigan 48106
THIS DISSERTATION HAS BEEN MICROFILMED EXACTLY AS RECEIVED.
X1BBABJ OF
HEW TORI DNIV1R8IW
DHIV1RSITY HEIGHTS’
Further Phase Studies of Sulfamates
In Aqueous Medium
A dissertation in the department of chemistry
submitted to the faculty of the Graduate
School of Arts and Science of New York University
in partial fulfillment of the requirements for
the degree of Doctor of Philosophy
by
Bernard Selikson
1950
The author wishes to express his
gratitude toward the person whose
direction and inspiration were ever
present during the conduction of
this work - Professor John E. Ricci
To my wife
and
to my parents
without whose encouragement and assistance
this work would never have been completed.
Table of Contents
Introduction 5
Summary of Literature 6
General Discussion 15
Experimental
Preparation of Salts 39
Methods of Analysis 48
Solubility Measurements 61
The System NaS - NaCl - H20 at 25° 65
The System NH43 - NH4C1 - H20 at 25° 70
The System NH43 - (NH4)2S04 - H20 at 25° 73
The System KS - KC1 - H20 at 25° 77
The System KS - KI - H20 at 25° 80
The System KS - K2S04 - H20 at 25° 83
The System NH43 - KS - H20 at 9°, 25° and 45° 8b
The System (NH4)2S04 - K2S04 - H20 at 25° . 103
The System NH45 - K2S04 - H20 at 25° 106
Summary 132
Bibliography 133
Introduction
Although sulfamic acid and its salts are finding
increasing use both commercially and in the laboratory,
relatively little information is published concerning
this family of compounds. The purpose of this research
is to extend the information, particularly with regard to
the aqueous solubility of the salts in the presence of
other salts, and also in the presence of their hydrolysis
product (namely sulfate) in order to obtain a clearer
picture of the purification process and in order to
classify better the behavior of the salts, thereby obtain
ing by comparison with other similarly behaving systems,
more information concerning the nature of the sulfamates.
There is presented here a report on the aqueous solu
bility relations at 25°C. of the ammonium, potassium and
podium sulfamates in the presence of the corresponding
chlorides; the system potassium sulfamate - potassium
iodide and water; and as part of the investigation of the
reciprocal salt pair ammonium sulfamate - potassium sul
fate in water at 25° (which is also reported here), the
ternary systems ammonium and potassium sulfamates with
corresponding sulfates and water (all at 25°), and at 9°,
25° and 45° the system ammonium sulfamate - potassium
sulfamate - water.
Summary of Literature
Sulfamic acid is reported^-»^ ^ and was found4- to be
a colorless, odorless, non-volatile, non-hygroscopic
solid, forming rhombic plates5, melting at 205° with
decomposition (Oberhauser and Urbina^ claim that it re
quires 209° to decompose the melt). It has a specific
gravity in toluene of 2.126 at 25° and in ether of
2.03 at 12° 3,5,8^ yields ammonium acid sulfate by
hydrolysis, reacts vigorously with nitrites to liberate
nitrogen and sulfuric acid, and also reacts with con
centrated nitric acid to yield nitrous oxide and sulfuric
acid^. It is reported as being isomorphous with its
potassium salt, as being less soluble than its salts, and
as crystallizing better from aqueous solution than most
of its salts8. It is suggested as a primary standard^
because of its high equivalent weight, (its strength
approaching that of hydrochloric and sulfuric acids-*-), and
because its hydrolysis would not change the titer of a
standard solution. However, the present writer finds this
suggestion unwise owing to the decomposition of wet sul
famic acid by heating, the requirement of obtaining sul
famic acid by desiccation rather than by heating, and the
necessity of storing the acid in a dry atmosphere to
avoid subsequent hydrolysis. If a really pure grade of
sulfamic acid were available, the suggestion would be
appropriate; as yet, it is not.
The solubility of the acid at 25° is listed by
7
Cupery0 in various solvents in grams per 100 grams of
solvent: methanol, 4.3 g.; ethanol (containing 2% ben
zene) 1.7 g«; acetone, 0.4 g.; ether .009 g.; formamide
20.0 g.. It is insoluble in hydrocarbons, chlorinated
hydrocarbons, carbon disulfide, and sulfur dioxide. The
aqueous solubility is decreased by sulfuric acid and by
sodium sulfate to insolubility at 70% sulfuric acid con
centration® »®, but it then rises again with further in
crease in acid concentration0. The solubility as a
function of temperature is listed per 100 grams of water:
14.08 g. at 0°; 18. g. at 10°; 21.32 g. at 20°; 20.09 g.
at 30°; 29.49 g. at 400; 32.82 g. at 50°; 37.10 g. at 00°;
41.91 g. at 70°; 47»08 g. at 80°. Two additional values
are given^: 14.94 g. acid per 100 cc of aqueous solution
at 12° and 40.00 g. at 78°; with the statement that
the increase in solubility with temperature is practi
cally linear. It is further noted that the pH of a 10$
solution is 1.8 as determined colorimetrically. Heating
the solid is inadvisable^ because at 135° the water is
"fixed", i.e.. hydrolysis takes place (this writer
observed this phenomenon at 110°) and at 105° the solid
does not become any drier than can be obtained by air drying
or by storing over Anhydrone. The present writer observed
that a saturated solution of sulfamic acid (approx. 2.5 Molar)
underwent measurable hydrolysis at 25° in several days.
This observation is in sharp variance with the findings
of Oberhauser and Urbina^-® that a Normal solution of the
acid is not hydrolyzed at room temperature over eight
months but is hydrolyzed at 97° to tfre extent of 24$ in
fifteen minutes and 30$ in one hour, and with their
statement that the degree of hydrolysis is higher in
more dilute solutions (and therefore probably lower in
more concentrated solutions).
They also report^ the preparation of the following
sulfamates by reaction with the corresponding hydroxides:
aluminum sulfamate, crystallizing with 18 moles of water -
m.p. 230°; calcium sulfamate tetrahydrate - m.p. 200°;
copper sulfamate dihydrate - m.p. 184°; potassium sul
famate - m.p. 211°; sodium sulfamate - m.p. 250°; zinc
sulfamate tetrahydrate - m.p. 195°; ammonium sulfamate -
128°; ferrous sulfamate with n molecules of water - m.p.
135°; nickel sulfamate tetrahydrate - m.p. 125°; by re
action with the corresponding chlorides; barium sulfamate
(does not melt under 300°); magnesium sulfamate tetra
hydrate - m.p. 91°; and by reaction with lead acetate:
lead sulfamate dihydrate (does not melt under 300°).
They further claim that the lead and barium salts are
insoluble in water, a statement which is inconsistent
with the properties of barium salt observed by this
writer and with the reported^>^ properties of both salts.
All the inorganic sulfamates reported in the literature
