938

0. BROOKS KING AND JOHN F. HOOPER

T H E SOLUBILITY IK WATER O F T H E BARIUM, CALCIUM, AND MAGNESIUM SALTS OF SULFAMIC ACID

G. BROOKS KIKG
AND

JOHN F. HOOPER'

Department of Chemistry, State College of Washington, PuZlman, Washington Received January $8, 1941

I n a recent survey of the literature of sulfamic acid and its salts, Gordon and Cupery (2) have pointed out a lack of fundamental data regarding the solubility of many of the sulfamate salts. Cupery has reported the solubility of the sodium, magnesium, calcium, barium, zinc, and lead salts a t 25C. and the solubility of the ammonium salt over the range of temperature 0" to 50C. I n general, the salts show an exceptionally high solubility. Further solubility data regarding these salts seem to be entirely lacking. It was the purpose of this investigation to determine accurately the solubility of the barium, calcium, and magnesium salts of sulfamic acid over a range of temperatures between 0" and 100C.
EXPERIMENTAL

Preparation and purification of materials Sulfamic acid. The acid used in the preparation of the salts was "Special Grade Sulfamic Acid," as furnished by E. I. du Pont de Nemours
and Company.2 The product was white and finely crystalline; its water solution gave no precipitate with barium chloride, but a test for the presence of iron with ferrocyanide solution was positive. Recrystallization of the acid to remove the iron was unnecessary, since the latter was removed during the preparation of the salts. Sulfamate salts. Essentially the same method was used in the preparation of the three salts. A slight excess of the carbonate of the metal, of analytical reagent grade, was slowly added to a water solution of sulfamic acid, Excess carbonate and the iron which had precipitated as hydroxide were filtered off, and the solution was concentrated by heating slowly on a hot plate, Barium sulfamate crystallizes as the anhydrous salt in radiating clumps of long white needles. Calcium and magnesium sulfamates crystallize as the tetrahydrates, the former in large, well-defined, arrowshaped crystals, and the latter in medium-sized, twinned, columnar crystals. The hydrates were stable in air a t ordinary conditions. The salts were recrystallized and showed a purity of a t least 99.8 per cent, as
1 This article represents a portion of a thesis presented by John F. Hooper t o the Faculty of the State College of Washington in partial fulfilment of the requirements for the degree of Master of Science. * The kindness of E. I. duPont de Neinours and Company in furnishing sulfamic acid for this research is gratefully acknowledged.

WATER-SOLUBILITY O F SULFAMATES

939

evidenced by analysis for t'he metallic ion. Cooling curves, determined for four different samples of the hydrate of calcium sulfamate gave the same t,ransition temperature within =tO.O5"C.
APPARATUS

An electrically controlled thermostat was employed for maintaining const,ant t,emperatures. The temperature was controlled within &0.05"C. up to 40"C., and within &O.lOC. up to 80C. Solubility determinations above 80C. were carried out in a small thermostat of about 2 liters capacity, in which a light mineral oil was used as t.he liquid medium. A wat,er-ice mixture was used to maintain a temperature of 0C. Solubility tubes consisted of 1 x 8 in. Pyrex test tubes, into which stoppers equipped with air-driven stirrers were fitted. 911 thermometers were calibrated against a Bureau of Standards thermometer.
VETHOD O F PROCEDURE

Equilibrium in the sat,urated solutions was approached from both unsaturation and supersaturation. I n preparing sat,urated solutions by the latter method, sufficient' salt, was dissolved in water a t a higher temperature than that a t which t'he solubility IYBS to be determined, so that a considerable excess of t'he solid phase would separate from the solution when cooled. Saturated solutions were prepared from unsaturated solutions by agitating an excess of the salt with water at t.he desired temperature. To test the establishment of equilibrium, samples were pipetted off from time to time, weighed, and analyzed, until successive samples gavc concordant, results. In general, equilibrium from supersaturated solutions was attained in a few hours, although in the case of the magnesium salt, at least 24 hr. were necessary. Samples prepared from unsaturated solutions required 48 to 72 hr. for establishment of equilibrium. To avoid crystallization of salt from solution a t the higher temperatures, i t was necesmry to heat the pipet above the temperature at which the solubility was being determined. At the lower temperatures, where the high viscosity of some of the solutions, notably magnesium sulfamate, greatly retarded the set,tling of fine salt crystals, a piece of filter paper fitted over the tip of the pipet prevented the entrainment of particles of solid. Suitable portions of the solution were analyzed by determination of the metallic ion of the salt. Barium was determined as sulfate; magnesium was precipitated as magnesium ammonium phosphate, followed by ignition to the pyrophosphate; calcium was precipitated as oxalate, followed by titration with permanganate. The above procedure was unsatisfactory for the determination of solubilities above SO'C., since it was difficult to maintain the pipet at a tern-

940

G. BROOKS KING AND JOHN F. HOOPER

perature high enough to prevent crystallization of the salt. Also, equilibrium conditions were disturbed because of condensation of water in the solubility tubes. Because of these difficulties, solubilities a t the higher temperatures were determined in a sealed tube. Weighed quantities of analyzed salt and water were introduced into soft-glass tubes and the tubes sealed off. The tubes were then introduced into the thermostat and agitated vigorously, while the temperature was raised a t a rate of approximately 0.1 per minute. The temperature a t which the last crystal dissolved was taken as the saturation temperature. Several deTABLE l Solubility of the baraum, calcium, and magnesium salts of sulfamzc acid
SOLUBILITY IN QRAYS OF ANEPDROUS SALT PER 1M) Q . OF WATER TEMPERATURE

_~~______ I--____

Barium salt

Calcium salt

Magnesium salt

WATER-SOLUBILITY OF SULFAMATES

941

The stable solid phase in equilibrium with saturated solutions of barium sulfamate is the anhydrous salt over the entire range of temperatures studied. A distinct break appears in the solubility curve for the calcium salt, indicating a change in phase. The transition temperature was determined by means of a typical cooling curve. Several determinations showed a transition point at 69.40'C. & 0.05'. Below the transition temperature, the solid phase is the tetrahydrate. Above this temperature, samples of the solid phase withdrawn and dried between

TfMP!RATU+?

OC:

FIG.1. Solubility of salts of sulfamic acid

filter paper showed varying ratios of less than two molecules of water to one molecule of anhydrous salt. The solid which had been dried in an oven a t 90' to 100OC. for 1 hr. proved to be the anhydrous salt. It seems likely that the stable phase above the transition point is the anhydrous salt. The solid phase in contact with saturated solutions of magnesium sulfamate is the tetrahydrate over the entire range of temperatures studied. By interpolation a t 25C. from the solubility curves obtained in this investigation, a comparison can be made of the solubilities of the sulfa-

942

G . BROOKS KIXG 9 X D JOHN F. HOOPER

mates of barium, calcium, and magnesium with those reported by Cupery (1) a t this same temperature. Results are shown in table 2. Considerable variation is to be noted in the results obtained in the two investigations. It seems likely that the results of the present inrestigation are accurate within very narrow limits, since equilibrium conditions were attained from both supersaturated and unsaturated solutions.
TABLE 2 Solubilities of sulfamates at 9 V C .
I

.___

. _

, SOLUBILITY I N GRANS OF ANEYDROUS SALT PER

SULFAMATE SALT

100 G . OF WATER

__-_______ Calcium Barium Magnesium

Cuper)
-

I
1

Present investigation

..-'--67-,78 0
3-1 2 119 29 7 110

__

SVTJIJISRY

1. The solnbilities in water of the barium, calcium, and magnesium salts of sulfamic acid have been determined as follows: calcium sulfamate between temperatures of 0" and 95.O"C.; barium sulfamate between temperatures of 0" and 100.2"C. ; magnesium sulfamate between temperatures of 0" and 80.0"C. 2. The transition temperature of calciuni sulfamate tetrahydrate into a second phase, probably the anhydrous salt, was found to be 69.4OoC. f 0.05".
REFERESCES (1) CUPERY: Ind. Eng. Chem. 30, 627 (1938). (2) GORDON K D CUPERY: A Ind. Eng. Chem. 31, 1237 (1939). (3) SIMMONS DROPP: J Am. Chem. Sac. 60, 1650 (1928). .~N