ON THE MERCURY NITROGEN COMPOUNDS - Journal of the

ON THE MERCURY NITROGEN COMPOUNDS

35

are brought together, no reaction takes place even a t elevated temperatures or under strong pressure. Several tubes containing these substances were allowed to stand for a year but at the end of this time no reaction had taken place. T h e two when heated together in tubes of very heavy glass, which had been obtained for work of this character, would not react, all of the tubes exploding when the temperature was sufficiently raised, but without previously showing any signs of change in the contents. After numerous attempts to bring the two to react the dioxide of selenium was vaporized from a porcelain boat in a glass tube in the vapor of sulphuryl chloride, and was condensed in a cooler portion of the tube. Analysis of the sublimed dioxide showed it to be chlorinefree, thus showing that it is possible to sublime selenium dioxide in the vapor of sulphuryl chloride without any reaction taking place. CHEMICALLABORATORY, UNIVERSITY OF WISCONSIN.

ON THE MERCURY NITROGEN COMPOUNDS (THE MERCURIAMMONIUM SALTS A N D BASES)

EDWARD C. FRANKLIN Received Xov.

23, 1906

Notwithstanding the considerable attention which has been given to the study of the mercury nitrogen compounds, widely diverse views are still held concerning their constitution as will be evident from consultation of the dictionaries of chemistry, scarcely any two of which agree in their methods of formulating these compounds. Most frequently, however, they are assumed to be substituted ammonium bases and salts. According to the view of Rammelsberg, which has been followed by Fehling and by Dammer in their classification of the mercury nitrogen compounds, and which in recent years has been defended especially by Pesci’ and his pupils, and also by RBy,’ all the mercury ammonia compounds are referred to the one type of mercuriammonium compounds in which the four ammonium hydrogen atoms of an ammonium salt are substituted by two atoms of mercury as indicated, for example, by the formulas, Hg,NOH and Hg,NCl, for dimercuriammonium hydroxide and chloride respectively. According to Pesci the salts of dimecuriammonium are especially prone to the formation of hydrates, and to union with ammonium and mercuric compounds to form double and complex salts. I n accordance with this theory the well known fusible white precipitate is given the formula, Hg,NCl. 3NH4C1; the infusible precipitate, the formula, Hg,NCl.NH,Cl; the chloride of Millon’s base, the l

Handworterb. Chem. (1890) 5 , 1091. Handb. anorg. Chem. ( 1894) 2.2, 896 and (1903)4, 630. 2. anorg. Chem. 21, 361. Ibid. 33, 193 and J. Chem. SOC.81, 645.

36

EDWARD C. FRANKLIN

formula, Hg,NCl. H,O; the ammoniated mercuric chloride, HgCl,.SH,, the formula, Hg,NC1.2HgC1,.3NH,Cl; and Kane’s salt, the formula, HgJNO:,. zSH,NO,. 2H,O; to illustrate by a few of the best known coinpounds. According to other vie1v.s all tlie mercury nitrogen compounds are formulated as substituted ammonium salts and bases, but differ froni the Ranimelsberg-Pesci theory in that a considerable number of types is assumed to exist. For example, the above enumerated compounds are i n other places ’ found formulated respectively as niercuridiamnioniunlini chloride, Hg( SH:,Cl),; as mercurianimonium chloride, H g S H , C l ; as osydiiiiercurianimonium chloride, S H , (HgOHg) C1; as a double salt of mercuridianimoniuni chloride and mercuric chloride, HgS,H,,CI,.Hg C,l ; and as a hydrated double salt of ox!-diiiiercuriamiiionium nitrate and ammonium nitrate, NH,!HgOHg)S0,.29H,”,O. According to still other views’ the conipoaiids of the type of the fusible and infusible white precipitates are removed froni the category of substituted amnioriium salts and are formulated respectively as inercury amines a n d arnidoriiercuric compounds, leaving the saits of hlillon’s base and related compounds to be formulated in accordance n.ith the theory that they are substituted ammoniuni salts. I t has been proposed by tlie writer .I to reject the substituted animoniuni theory entirely as applied to the so-called mercuriammonium conipouiids and to substitute therefor a modified and extended form of Kane’s old auiide theory. Accordingly the attempt is made here to show that many of these substances are, in fact, compounds related to ammonia as the ordinary basic salts are related to water, they are ammonobasic salts; others are compouiids which are basic at the same time to both ammonia and water, they are niised ainmonobasic-hydrobasic salts; while still others are simply tnercuric salts with ammonia of crystallization. T H E A3lMbIONIA SYSTEM 01: A C I D S , BASES A S D SALTS.

I n earlier papers Frankliu aiid Kraus have called attention to the striking properties of liquid ammonia as a solvent. S e x t to water, i t has been found to possess the widest soivent power of any liquid so far investigated. I n its tendency to unite with salts and other compounds, it probably exceeds water, since salts with ammonia of crystallization are, perhaps, even more numerously recorded i n the literature than are salts with water of crystallization. It is coiispicuous for the facility with which Grneliii-Kraut: Hanclb. anorg. Chem. ( ~ S i j )3, S I S - S ~ O . Ii’atts: Dict. Chem. (1892) 3 , 206.212. Ladenburg; Handworterb. Chem. (1892) I O , 148-163. ? Allegg: Handb. anorg. Chem. 2.2, 666. Cf. Ginelin-Kraut: Watts: Ladenburg: 1. c. This Journal, 27, 827. Am. Chem. J. 2 0 , 8 2 0 ; 21, 8; 23, 27;; and this Journal, 27, 191.

37

O N THE MERCURY NITROGEN COMPOUNDS

many of its solutions carry the electric current, and especially to be noted is the fact that in its general, chemical and physical properties it shows a striking resemblance to water. A m m o n o acids, A m m o n o bases ana’ A m m o n o salts. Following up the analogies between water and ammonia indicated in the papers above cited, Franklin and Stafford’ were able to show that the acid amides and the metallic amides, which are formally related to ammonia, as the ordinary acids and bases, respectively, are related to water, as a matter of fact act toward each other, in solution in liquid ammonia, in a manner strictly analagous to the familiar interaction of acids and bases in aqueous solutions. This relation is shown in the equations, CH,COO’ H K * OH’ = CH,COO’ K * H,O CH,COE”’ H * K * NH,’ = CH,COKH‘ K * NH, for the water and ammonia systems, respectively. In a later paper by the writer,2 the ammonia system of acids, bases and salts was further elaborated, and the proposal was made to refer to the acids, bases and salts of the ammonia system, that is, to the acid amides, the metallic amides, and to the metallic derivatives of the acid amides respectively, as ammono acids, ainmono bases and ammono salts. Ammonobasic Salts. I n the paper last cited, the writer has shown that ammonia acts upon certain metallic salts in a manner analogous to the familiar hydrolytic action of water. T h e compounds thus formed are related to ammonia exactly as the ordinary or “ hydrobasic ’’ salts are related to water, for which reason the writer has ventured to refer to such con~poundsas ammonobasic salfs, and to use the adjective ammonolytic to describe the action whereby they are produced. I t has been shown, for example, that the reversible equations,

+ +

+

+

+ zNH, + NH,HgCl + NH,Cl, Hg : N - H g - I + 3NH,I, zHgI, + 4NH, (3) zPbI, + 5NH, + NH, - Pb - X H - Pb -I $. 3NH,I,

( I ) HgCI, ( 2 )

and represent what takes place’when the salts indicated are treated with liquid ammonia. T h e salts are ammonolyzed by the solvent, giving insoluble ammonobasic salts and setting free the respective halogen acids in the form of their ammonium salts. Ammonobasic Mercuric SaZLs. Now it happens that most amniono bases, ammono salts and ammonobasic salts, for example potassium amide, KNH,, magnesium acetamide, (CH3CONH),Mg.4NH,, and the ammonobasic lead iodide, NH,PbNHPbI, are completely hydrolyzed in the presence of water, from which it follows that such compounds, in general, can be formed only from aninionia solutions, or in any event, only Am. Chenl. J. 28, 83.

This Journal, 27, 820.

38

EDWARD C. FRAKKLIN

in the presence of solvents other than water. T h e compounds formed by the action of ammonia on mercuric oxide or on the salts of mercury, are, however, an exception to this rule. They are capable of existence in the presence of water, and, as a consequence, many aninlonobasic mercuric compounds have been made in the past and are found described in the literature under various names, for the most part, however, as mercurianimonium compounds.

Mixed Ammono6asic-Nydro6nsic Mercuric Salts. In addition to their undergoing ammonolysis, mercuric salts, generally speaking, are also SUSceptible to hydrolysis, T h e halogen salts, excepting the fluoride, and the ammono salts are but slightly hydrolyzed, while the hydro salts are highly hydrolyzed in aqueous solution. In a mixture of water and ammonia, in addition to the amtnoriolytic action of the ammonia, the normal hydrolytic action of the water is accentuated by the increased concentration of the hydroxyl ions, due to the presence of ammonium hydroxide. W e might therefore expect the formation of products which are at the same time basic both to water and ammonia, and as a matter of fact this class of compounds is very numerously represented among the known mercury nitrogen compounds. THE PRECIPITATES A N D THE CHLORIDE O F JIILLOS'S

RASE.

T h e fusible white precipitate is mercuric chloride with ammonia of crystallization, HgC1,. 2NH, ; the infusible precipitate is an ammonobasic mercuric chloride, NH,-Hg-CI ; and the chloride of Millon's base is a mixed hydrobasic-ammonobasic mercuric chloride, HO-Hg-SH-CI, or NH,-Hg-0-Hg-C1. These formulas are in accord with the ideas held over sixty years ago by Kane,' concerning the constitution of the compounds under consideration, for he clearly points out the fact that the fusible white precipitate is one of a large number of compounds, in which amnionia plays a part analogous to that of water in salts containing water of crystallization ; he recognized that the infusible white precipitate is a compound, related to ammonia as an ordinary basic salt is related to water, and he also observed that the yellow salts, later known as salts of Millon's base, are compounds resembling basic salts. Although for many years Kane's theories have been entirely ignored, his method of formulating the white precipitates has nevertheless been followed to a greater or less extent since the promulgation of his views. Especially has his formula for the infusible white precipitate been emphasized in recent years by Hofmann and Marburg' and by Fiirth' who A n n . chim. phgs. 72, 337. Ann. 305, 194; Z.'ariorg. Chexn. 23, 126. Monatsh. 23, 11.1;.

ON

THE

MERCURY NITROGEN COMPOUNDS

39

give conclusive evidence of the correctness of Kane's formula and of the inadequacy of the Rammelsberg-Pesci formula.' T h e writer's view of theconstitution of the white precipitates and the chloride of Millon's base is certainly justified by their methods of preparation, by their general properties, and by the manner in which they are mutually converted into each other. T h e fusible white precipitate is formed by the direct addition of ammonia to mercuric chloride when the latter is treated with liquid ammonia. I n the presence of an exce'ss of the liquid, ammonolysis takes place resulting in the conversion of a small portion of the salt into the infusible precipitate, the quantity of which may be increased at pleasure by the addition of an alkaline amide. Inversely the infusible precipitate is converted into the normal salt by the action of a liquid ammonia solution of ammonium chloride.2 Entirely similar changes take place in aqueous ammonia solutions, excepting that here, as the concentration of the ammonium chloride becomes very small, the hydrolytic action of the water is superimposed upon the ammonolytic action of the ammonia. Various investigators have repeatedly observed that the fusible white precipitate is stable only in the presence of a considerable concentration of ammonium chloride, that when it is vashed with water it is converted first into the infusible white precipitate and finally, after long washing, into the chloride of Millon's base. Contrarywise. by digestion with ammonium chloride solution the latter compound is changed first into the infusible white precipitate and then into the fusible precipitate. T h e action of water on the white precipitates, and the inverse action of ammonium chloride solution on the chloride of Millon's base and on the infusible precipitate, which are represented by the equations, HgCl,.ZNH,+NH,-Hg-Cl NH,C1 ZNH,-Hg-Cl+ H,O+HO-Hg-NH-Hg-CI NH,Cl, are therefore phenomena which are very like the formation of ordinary basic salts by the action of water on normal salts, and the reconversion of the former into the latter by an excess of acid.3

+

+

Cf. however, Pesci: 2. anorg. Chem. 21, 361. Franklin: This Journal 27, 841. 3 I t has been shown that in liquid ammonia solutions ammonium salts exhibit a behavior which in many respects is very siniilar to t h e action of acids in aqueous solution. (Franklin: this Journal, 27, 822.) I t is not surprising therefore that in certain cases a siniilar action should take place i n aqueous solutions. I n addition to t h e above described reactions, t h e well known solubility of zinc and magnesium and of certain metallic hydroxides in aqueous solutions of ammonium salts, the hydroxides of magnesium and calcium, for example, may be mentioned as illustrative of the acid properties of such solutions.

40

E D W A R D C. F R A N K L I N

A study of the above equations in accordance with the principles of the Phase Rule, as first suggested for the identification of ordinary basic salts, by Miller and Kenrick,’ and applied by Allen’ and by Cox,Rwas begun in this laboratory but unfortunately lias been interrupted for the time being by the recent earthquake. T h e work so far has shown that the ~ W O C O I I ~ ~ O U I I ~ S HgC1,.2?;H, and T\”,-Hg-Cl are mutually in equilibriurn with a 0.49 normal aqueous solution of anixnoniuiii chloride. A11 that can be said a t the present tinie concerning the concentration of amnioiiiunl cliloritle in the second equation is that it is very much lower than iti the first equation. Among the characteristic properties of ordinary basic salts are their insolubility, their generally amorphous character, and their tendency to form mixtures of indefinite composition. Similarly the infusible white precipitate, the chloride of LIillon’s base, and the mercury nitrogec preparations classified in the later pages of this paper have been obtained generally as insoluble, arnorplious precipiitates, while in the manner in which various obviously complex mixtures of the mercury nitrogen compounds have been reported as clieniical individuals, the analogy between the latter and the ordinary basic salts is further exemplified. h l I L L O N ’ S Ilr\SE A N D ITS D E H Y D K . 4 T I O N PKODUC’I’S

T h e so-called Millon’s base, Hg,NH,O,, has been prepared and studied by numerous investigators,4 and has been represented by no less than seven different formulas depending upon the view intended to be expressed concerning its constitution. Generally > however, the base and its dehydration products have been formulated as substituted m m o n i u r n hydroxides. In accordance with the view of the writer Villon’s base and its dehydration products are best accounted for by assnming them to be mixed aninionia water bases; that is they are compounds which are basic a t the same time to both ammonia and water T h e amorphous character of these bases and their insolubility are in harmony with this assumption concerning their constitution as is also their behavior toward acids. As dilute acids convert certain of the hydro bases into hydrobasic salts while more concentrated acid solutions change them into neutral salts, so also do acids” or ammonium salts, depending upon the concentration, J . physic. Clieni. 7, 259. Am. Chem. J. 25, 307. ,‘I %. anorg. Cheni. 40, 146. Gnielin-Kraut: Handb. anorg. Chem. ( r S 7 j ) 3 , 875; Hofmann and Marburg: -4nn. 305, 240. 3 Lndetlburg: Handworterb. Cherri. ( rS92) I O , 156; Hofrtl.inn and Narburg: loc. cit. F u r t h : Monatsh. 23, 1147. ‘j S i t r i c acid and sulphuric arid dissolve the salts of Millon’s base o t ~ l y in the presence of a small quantity of ammonium chloride. (Pesci: Z. anorg. Chexrl. z1,;6S. )

,’


41

convert these bases into mixed ammonobasic-hydrobasic salts, into ammonobasic salts or into neutral salts. As is well known, Millon’s base is formed by the action of ammonia on mercuric oxide. I t seems worth while to emphasize here the view that the action of ammonia on mercxric oxide is analogous to the ordinary hydration of a metallic oxide to form an hydroxide, and is due in the present instance to the well known tendency of mercury to replace hydrogen in many of the derivatives of ammonia. Just as water, for example, reacts with calcium oxide to form calcium hydroxide, so ammonia, in the absence of water, unites with mercuric oxide to form, not as might perhaps be expected, the mixed hydro ammono base, HO-Hg-WH,, but the deammoniated product of this compound, HO-Hg-NH-Hg-OH. In the presence of water a product is formed containing an additional molecule of water, namely, Millon’s base. Millon’s base is therefore better represented by the formula, HO-Hg-NH-Hg-OH.H,O, or perhaps rather by the formula of Hofmann and Marburg, ( H O H g ) , N H , O H , or of Fiirth, HO-Hg-0-Hg-”,OH, than by any others which have so far been suggested. Hofmaiin and Marburg’ formulate the dehydration of Millon’s base in accordance with the equation, HO-Hg )“,OH o/Hg>HzOH H,O, HO-Hg “g and express the opinion that the basic properties of the compound are due to the ammonium hydroxyl. T h e writer on the contrary believes that the formula for the dehydration product is rather HO-Hg-NH-Hg-OH, and that in both compounds the basic properties are due, not to the ammonium hydroxyl, but to hydroxyl in combination with mercury. I t is a well known fact that the hydroxyl group attached to mercury exhibits strong basic properties while so far as the present writer knows, there is no certainty of the existence of nietallic derivatives of ammonium hydroxide from which conclusions can be drawn concerning the strength of such bases. Furthermore in view of the slight ionization of the mercury halogen compounds and the consequent marked tendency of halogen ions to unite with mercury ions, it is difficult to believe that a compound of the formula,

-

ONH2Cl,

+

as required by Hofmann and Marburg, rather than one

of the formula, HO-Hg-NH-Hg-C1, would be formed when the base is treated with dilute hydrochloric acid.’ Ann. 305,

204.

* It must be admitted that

the formula, (HOHg),NH,OH, while in harmony with the above considerations, nevertheless represents the base as a substituted ammonium hydroxide. Its properties as such, however, are entirely inconspicuous and are subordinate to its properties as a mercury base.

42

EDWARD C. FRANKLIN

As a mercury base the second dehydration product of Millon’s base, which has usually been formulated as dimercuriammonium hydroxide, Hg,X-OH, can scarcely be otherwise represented than by the formula, Hg:N-Hg-OH, while the formulas of either Hofniann and Marburg, ( H O H g ) , N H , O H , or of Fiirth, HO-Hg-0-Hg-XH,OH, for iMilloll’s base and either HO-Hg-NH-Hg-OH, or HO-Hg-0-Hg-NH, for the first dehydration product, seem equally applicable. T h e adoption of the formula, Hg: PI;-Hg-OH, for the second dehydration product, however, permits a choice to be made between the forniulas for the other two conipounds, from the fact that the mechauism of the dehydratim is the more readily explained if the formulas, ( H O H g ) , F H , O H and KO-Hg-NH-Hg-OH, are used. T h e dehydration of Millon’s base is therefore represented as follon5, HO-Hg ,O-,,>

NH.H,O

(Millon’s base )

HO-Hg-NH-Hg-OH (First dehydration product.)

%Hg

=:

N-Hg-OH.

(Second dehydration product.)

MEKCCRY DERIVATIVES OF THE SUBSTITUTED ANMONIBS.

Hofmann and Marburg’ have already called attention to the fact that the mercury derivatives of the alkylaniines cannot be formulated in accordance with the theory of Ramnielsberg and Pesci, and that since such cornpounds as HgC1,. 2C,H,NH, and C,H,rU”-Hg-Cl, are obviously the ethylamine analogues of the fusible and infasible white precipitates respectively, it follows that the formulas, Hg,NC1.3h’H4C1 and Hg,NCl.h’H,Cl, for the latter compounds mu5t be abandoned. It beconies a matter of importance therefore to enquire mhether the properties of the known mercury derivatives of the substituted amnionias, and the methods by which they are prepared are in harmony with the theory made use of in this paper for the systematization of the mercury ammonia compounds. It may be said at once that such is i n fact the case. T h e ethylamhe analogue of the fusible white precipitate ha5 been made by the action of ethylaniine on a solution of mercuric chloride containing hydrochloric acid’ ; the analogue of the infusible precipitate, by the action of ethylamine on a solution of mercuric chloride in the absence of any excess of hydrochloric acid ; while the ethylamine analogue of the chloride of Millon’s base ha5 been prepared by adding ethylamine to a solution of mercuric chloride and boiling the precipitate formed with a large excess T h e conditions necessary for the formation of these three of water. compounds are thus seen to be identical with those which give the three corresponding ammonia derivatives. Below a certain concentration of Ann. 305, 201. I-Iofmann and Marburg. Ann. 305, zoz Koliler: Ber 12, 2208-2321.


43

ethylamine hydrochloride the mercuric chloride with ethylamine of crystallization undergoes ‘ I aminolysis ” to form an I ‘ aminobasic ” salt, while a t high dilution, that is by digestion with much water, simultaneous hydrolysis and “ aminolysis ” convert the “ aminobasic ” product into a mixed hydrobasic-aminobasic ” salt. T h e ethylamine analogues of the white precipitates and of the chloride of Millon’s base may therefore be given the formulas, HgCl,. 2C,H,NH,, C,H,NH-Hg-Cl and HO-Hg-NC,H,-Hg-C1 respectively. Among other mercury derivatives of the substituted ammonias two of the benzylamine mercury compounds,’ the sulphate, (C,H,CH,NH-Hg),SO,, and the acetate, C,H,CH,NH-Hg-C,H,O,, are especially interesting for the reason that they are oxygen acid salts of the type of the infusible white precipitate, a class which is unrepresented among the known ammonia derivatives. Many mercuric salts with aniline of crystallization have been prepared as have also the aniliue analogues of the infusible white precipitate, C,H,NH-Hg-CI,’ and of the chloride of Millon’s base, HO-Hg-C,H,NHg-Cl’. T h e characteristic properties of ammonia and the amines in forming the various mercury compounds as discussed in the preceding pages are exhibited also by other nitrogen compounds. For example, pyridine and quinoline unite with mercury salts as pyridine and quinoline of crystallization‘ but d3 not form compounds corresponding to the ammonobasic salts ; benzamide forms the “a~nidobasic’’~ iodide, C,H,CONH-Hg-I ; succininiide forms the compound,‘ CH2Co)N-Hg-CI. CH,CO form-,b-toluide form

compounds of

the

type,’

formanilide and CHO Ar)N-Hg-Ac

;

while urea reacts with mercury salts’ to give such compounds as HgCI,.CO(NH,),, mercuric chloride with urea of crystallization; Pesci: Z. anorg. Chem. 15, 224. Forster: Ann. 1 7 5 , 25. 3 Furth: Monatsh. 23, 1157. 4 2. anorg. Chem. 1 5 , 225. Bruni and Manuelli, 2. elekt. Chem. XI, 554, 5 Tafel uiid Enoch: B. 23, 1554. have called attention to certain reactioiis for which they have proposed the name “amidolysis.” 6 Menschutkin: Ann. 162,172;Ley und Schaefer: 2. physik. Chem. 42, 696. Wheeler and McFarland: Am. Cheni. J. 18,543. Ruspaggiari: Jsb. Chem. 1897, 1577; Pesci: 2. anorg. Chem. 15, 232. Ruspaggiari recognizes t h a t these compounds are t h e urea analogues of the well known mercury ammonia compounds a n d assumes in accordance with the RammelsbergPesci theory that they are salts of the divalent radical, mercuriurea, CO(NHgH),.

44

EDWARD C. FRAXKLIX

co/

XH-Hg-NO,

S H Hg-C1

co’

XH-Hg-XO,

\sH-H~-Ko,’ NH-Hg , and CO( )SO,, Co( HgC1),.7Hg : P-Hg-C1 and P(HgCl),.Hg : P-Hg-C1, while Franceschi’s conipound, ASH(HgCl), is the arsenic analogue of the animonobasic salt, XH(HgCl),. CLASSIFICATION O F T H E MERCURY NITKOGES COAIPOUNDS.

I n accordance with the theory above outlined the writer proposes in this paper to classify the mercury nitrogen compounds found described in the literature under the following groups arid to give under each compound such brief data concerriing its preparation and properties as are necessary to show that, without exception, all the compounds which have been prepared are readily to be brought into this scheme of classificatiot~.

I.

AAIhIONO BASES AND MIXED HYDRO A M M O N O BASES O F CRYSTALLIZATION AND W I T H AMMONIA AND WATER O F CKYSTALLIZATION. 111. AMMONOBASIC NERCURICSALTS, which include the aninionobasic

11. BIERCURIC SALTS WITH AJIMOKIA

halogen salts, the ammonobasic hydro salts and the ammonobasic ammono salts. Adams: . h i . Cheni. J. 28, 198. Hofrnann und Marburg: Ber. 30, 2019 and Ann. 305, 2 ~ 4 . Aschaii: J. Chem. SOC.5 0 , 423, Partheil und Amort: Her. 3 1 594. ~

45


IV.

MERCURIC SALTS, which may likewise be salts of either the hydro acids, the halogen acids or the ainmono acids.

MIXED AMMONOBASIC-HYDROBASIC

MERCURY BASES

I n the list of compounds indicated in the table which follows are given in the first column the purely empirical formulas. I n the second column each compound is formulated as a basic mixture. T h e formulas given here are, as a matter of course, more or less arbitrary-the compound ( 4 ) , for example, may be given any one of a half dozen or more possible formulas-but seem to be worth the space given them in view of their bearing on the theory of the writer concerning the constitution of these compounds. I n the third column the structiiral formulation of the simpler compounds only is attempted for the reason, principally, that the more complicated formulas, in all probability, do not represent definite compounds. TABLEI. I.

Hg,N, 2 . HgNN,O 3. Hg,NHO 4. Hg,NH,O, 5. Hg,NH,O, 6. Hg,NHO, 7 . Hg,N,O 8. H g J , H , O , 9. Hg,N,H,O, IO. Hg,N,H,,O,

11.

I.

HgO.NH, 13gO.HgNH zHgO.NH, zHgO.NH,. H,O 2HgO.HgNH HgO.Hg,N, 3HgO.Hg (NH,), 4Hg0.zNH3.H,0 6Hg0.3NH3.2H,0

111.

Hg:N-Hg-N : H g HO-Hg-h”, H g : N-Hg-OH HO-Hg-NH-Hg-OH (HO-Hg),NH.H,O H g N-Hg-0-Hg-OH ( H g : N-Hg),O

I . Hg,N,. Neither cf the theoretically possible ammono bases, mercuric amide, Hg(NH,),, nor mercuric imide, H g N H , is known.’ The reactions which might be expected to give one or the other of them, namely the action of potassium amide on a mercuric salt in liquid ammonia, gives as a matter of fact the final deamnioniated product, Hg,N,.* 2. HgNH,O. Watts’ Dictionary is in error in giving a compound of the formula, HO-Hg-h”,, as a product of the action of ammonia on mecuric oxide. Compounds of this type are however known, as for example, the urea derivative, NH,CONH-Hg-OH,’ and Pesci’s so-called mercuribenzylammonium hydroxideJ6 C,H,CH,NHHg-OH.

T h e aniline compound ( C,H,NH),Hg, corresponding to mercuric amide h a s been prepared. Pesci: 2. anorg. Chem. 15, 213. Franklin: This Jouriial 28, 835. T h e doubts expressed by Hofrnann and Marburg ( A n n . 3 0 5 , 193 and 210) and repeated by Ley (Abegi Handb. anorg. Chem 2.2, 675) concerning the existence of this conipound are therefore removed. Ed. 1892,3, 207. Cf. Ann. chim. phys. 72, 225. * Beilstein: Handb. organ. Chem. (1893) I , 129j. Z.anorg. Chem. 15, 224.

46

EDWARD C . F R A N K L I N

3. Hg,NHO. This compound is obtained as an explosive, brown powder by heating Millon’s base in an atmosphere of ammonia.’ I t is usually formulated as diniercuriammoniuni hydroxide, H g , S O H or (Hg)XH, Hg and (Hg,N),O.H,O. Fiirth2 has proposed the formula, 0

Hg

1 )N - O H . Hg 4. Hg,NH,O,. A brown, amorphous powder of this composition has been obtained by various investigators, most recently by Hofmann and Marburg,4 by drying Millon’s base in an atmosphere of ammonia. WeyP obtained a yellow coinpound of the same composition by treating yellow mercuric oxide with dry gaseous ammonia or with alcoholic animonia. I n the dictionaries of chemistry this compound is found formulated as a hydrated dimercuriamnionium hydroxide, Hg,NOH.H,O, or (Hg,N),O. gH,O, or as oxydimercurianinionium hydroxide, (HgOHg)NH,OH. Fiirth gives i t the formula, KH,HgOHgOH HOHg and Ranimelsberg the very unlikely formula, )NOH. “g j. Hg,NH,O,,. This is the well known Millon’s base which isobtained most readily by the action of aqua ammonia on freshly precipitated mercuric oxide.‘ Fiirth‘ has recently shown that Millon’s base is also formed by the action of aniinonia on an aqueous solution of mercuric acetamide. T h e constitution of Millon’s base has already been discussed. 6. Hg,NHO,. Hofmann and Marburg” obtained a coinpound of approxiniately this composition by drying Millon’s base in uacuo over sulphuric acid. They give no analytical data and remark that the product is probably a mixture. 7 . Hg,N,O and 8. Hg,N,H,O,. These two dehydration products of Millon’s base, prepared respectively by WeyP and by Millon” should, in Rammelsberg3 the formula,

G-K: S16; Hofmann and Marburg: Ann. 305, 2 0 7 . The records given in Gmelin-Kraut’s Handhuch der anorganischen Chemie have been taken as representi n g the state of knowledge of the mercury nitrogen compounds a t t h e date of t h e publication of the sixth edition in 1875, I n the interest of brevity the frequent references which will be made to the third volume of this work will be shortened to a statement of the page preceded by the initials G-I(. Monatsli. 23, 1154. J. pr. Cheni. 146,5 6 2 . Ann. 305, 206. G-K: Sr6. G-K: SI?; Hofmann and Marburg: -4nn. 305, 206. Monatsh. 23, 1156. A n n . 305, 207. G-K: 815‘ lo Ibid. Sr6.


47

all probability, be stricken from the list of known compounds inasmuch as Hofmann and Marburg’ were unable to confirm the existence of either. 9. Hg,X,H,O, and IO. Hg,N,H,,O,. Gerresheim’s’ efforts to prepare Millon’s base led him to a product having the composition of the former of the preceding formulas, while Rammelsberg, found his preparation to have the composition represented by the latter. T h e fact that Millons’ base readily loses water to form the compound (4) page 46 may account for the results obtained by these investigators. AMMONIATED MERCURIC SALTS. MERCURIAMINES. MERCURIC SALTS W I T H AMMONIA O F CRYSTALLIZATION, OR WITH BOTH AMMONIA AND WATER O F CRYSTALLIZATION.

All the con~plexformulas which have been proposed for the various compouiids described below are avoided, and at the same time the behavior of these salts is much better explained, when it is assurhed that the members of the group are compounds in which the ammonia plays a part analogous to that of water in salts with water of crystallization. Any new knowledge of the function of water and ammonia in such compounds is distinctly disclaimed, and indeed such knowledge is beside the purpose of this paper. I t is sufficient here to insist on the removal of these compounds from the class of the so-called xnercuriammonium compounds and to recognize them as belonging to the large class of salts with ammonia of crystallization. T h e following salts, which have been found described in the literature, are here formulated as simple addition products. TABLE11. HgCl,.”, 12. 2HgCl2.3NH, 13. HgC1,.2NH, 14. H ~ C I , . I ~ N H , 15. HgC1,.2NH,.%HZ0 16. HgBr,.NH3 17. HgBr2.2NH, 18. HgI,.NH, 19. 3Hg1,.4NH3 20. HgI,.2NH, 21. HgI,.NH,.H,O 11.

22. Hg(CN),.NH3 23. Hg( CN),.2NH3 24. Hg(CN),.NH,.% H,O 25. Hg( CN),.2NH,. %H,O 26. Hg(N0,),.2KHS 27. HgS0,.2NH, 28. HgSO,. 2NH,. H,O 29. 2Hg( SCN),.3NH,.H,O 30. H g ( C,H,O,),.2NH,oHZO 31. HgCr,0,.2NH,. %H,O

I I. HgC1,. NH,.’ This compound has been prepared by passing ammonia gas over warm mercuric chloride,, by distilling mercuric oxide

’ 1. c.

Ann. 195,373.

J. pr. Chem. 146,561. It is interesting to note the unlikely formulas, (ClHg)NH,Cl; HgN,H,CI,. HgCI,;Hg,NCl.3NH4C1.2HgCl, ; and ( NHg~C1.NH,Cl).2(HgCl2.NH,Cl) ; which have been variously assigned to this compound.

48

EDWARD C. F R A N K L I N

with ammonium chloride,‘ by heating the infusible white precipitate,’ and by the action of ammonia gas on a solution of mercuric chloride in benzonitrile.” Damnier,‘ and Hofniann and Marburg’ have expressed doubts of the existence of such a compound. 12. 2HgClZ.3’NH,. Varet‘ obtained a product of this composition by the action of alcoholic ammonia on the double salt, HgCl,. Hg(CN),. 13. HgC1,.2NH3. This is the well known fusible white precipitate. I t was first definitely distinguished from the long known white precipitate of the pharmacists by Kane,’ who proposed for it the name, Wohler’s precipitate. Its preparation and properties have already been discussed.’ 14. HgCl,. I 2NH,. Franklin and Kraus ‘’ prepared this compound by the action of liquid ammonia on mercuric chloride. 15. HgCl,. ISH:,,.$H,O. By passing a current of ammonia gas through a warm solution of mercuric oxide in aqueous ammonium chloride or by the addition of this solution to warm aqua ammonia, Andre” obtained a product of this composition, I t is safe to assume that the existence of such a compound needs confirmation. 16. HgBr,.NH,. A compound of this composition has been obtained by the action of ammonia gas on melted mercuric bromide,” and a s a sublimate by heating the compound HgBrSH,.’, 17. HgBr,.2XH,,. PesciI2 has prepared this compoutid by the action of ammonium bromide solution on the amnionobasic bromides, qHg,NBr.gNH,Br (40) and NHg,Br (41), as well as by the action of aqua amnionia on a solution of mercuric bromide containing ammonium bromide. H e also obtained i t by the action of ammonia on an alcoholic solution of mercuric bromide. I 8. HgI,.NH,, z I , Hgl,. SH,,.H,O. According to Gmelin-Kraut”’ G-K : S ~ O . G-E; : 834. Sauniann : Ber. 32, 1000. Handb. anorg. Chem (1894) 2.2, 903. j A n n . 305, 2 0 2 . 6 Rti11. SOC. chim. ( 3 ) 6, 223. A n n . chim. phys. 72, 380. a \Veyl considers the compound formed by the action of liquid ammonia on mercuric chloride to be different from Wijhler’s precipitate and gives i t the formula, 2HgC1,.4NH,. ( G - K : 840) Franklin and Kraus ( A m . Ch. J. 23,300) were unable to distinguish Weyl’s preparation from t h e white precipitate obtained by other methods. Am. Ch. J. 23, 300. Weyl’s statement (G-K : 840.) to the effect that mercuric chloride is readily soluble i n liquid ammonia is an error. Liquid ammonia, in a closed tube, a t laboratory temperature unites with mercuric chloride to form a dense liquid which is but slightly soluble in excess of the ammonia. Compt. rend. 112, 860. G-K : S32. l 1 Jsb. Chem. 1890,629. Is G-K : 830.

‘

ON THE M E R C U R Y NITROGEN COMPOUNDS

49

the compound represented by the first of these formulas has been obtained by a number of investigators. Nessler's preparation contained from 3.2 to 3.5 per cent. water for which reason the second formula is found in the literature. Pesci's attempts ' to prepare the compound HgI,.NH, led him to a product to which he gave the formula, 3?JHg2I.qHgI,.8NH,I. Instead of a compound of this unlikely formula Pesci probably had in his hands a slightly animonolyzed mixture, g H g I,. xNH,. N H , H g I . I n view of the fact that FranGois,' by vapor pressure measurements, has proved the existence of the two following ammoniated mercuric iodides only, it follows that the earlier data pointing to the existence of the compound, HgT,.KH,, must be in error. 19. 3HgI2.4NH,. A colorless compound of this composition has been shown by Francois' to have a definite decomposition tension from which it follows that the formula must represent a chemical individual. 20. HgI,.2NH3. This compound has often been prepared by the action of ammonia gas, of aqua ammonia and of liquid ammonia on mercuric iodide.' I t is soluble in ether and in alcohol, in each case, however, leaving behind a yellow or brown residue, the result in all probability, of slight animonolysis of the salt. Its decomposition tension is considerable so that the compound rapidly loses its ammonia on exposure. T h e compounds 2 2 , 23, 24 and a 5 have been prepared by Varet5 by the action of ammonia on mercuric cyanide under various conditions.6 26. H g ( NO,),. 2NH,. Pesci' prepared this crystalline animonia addition product of mercuric nitrate by the action of a fifty per cent. solution of ammonium nitrate upon the mixed basic nitrate (73) and upon the hydrobasic nitrate, Hg(NO,),.HgO. This is an example of the conversion of a basic salt into a normal one by the action of a solution of an ammonium salt. 27. HgS0,.2NH,. Millon obtained a compound of this composition by saturating aqua ammonia with mercuric sulphate and evaporating J. Chem. SOC.60, 2 7 0 . Compt. rend, 129,296. loc. cit. ' G-K : 831; Pesci : Jsb. Chem. 18g0,6 3 2 ; Fransois : loc. cit. Bull. SOC. chin]. (3) 6, 220. 6 Franklin and Kraus also prepared the addition product, Hg(CN),.2NH3, Since their results were never published i t seems worth while to give their data here. Mercuric cyanide was dissolved i n liquid ammonia, after which t h e excess of liquid was allowed to evaporate. I n two experiments 1 . 1 9 gm. a n d 1.655gin. mercuric cyanide retained respectively 0.1465gm. and 0.2240 gm. ammonia. Calculated for Hg(CN),.zNH,, 11.g0per cent. ammonia. Found respectively, 10.pand 11.93 per cent. The compound readily loses its ammonia. Jsb. Chem. 1890,630. G-K : 825.

50

EDWARD C. FRANKLIN

the solution to dryness. Pesci,' following Millon's directions, obtained a product of the same composition which, however, he assumed to be a mixture. 2 8 . HgSO,. 2NH,. H,O. Schmieder' prepared this compound in the form of beautiful crystals by dissolving mercuric oxide in a solution of ammonium sulphate and evaporating the solution until a crop of crystals was obtained. Heated t o I 15' this compound loses its water.s Following Schmieder's directions, Pesci' obtained a compound of the same composition to which he gave the formula, (NHg,),S0,.3( NH4),S0,.4H,0." 29. 2Hg(SCN),.3NHs.H,0. Fleischer ' dissolved mercuric oxide in a hot solution of ammonium su!phocysnide when on allowing the solution to cool an ammoniated mercuric sulphocyanide separated out in well developed crystals. Analyses of different specimens showed a rather wide variation in the amount of ammonia and water present. T h e same, or a similar compound, was obtained by Ehrenberg ' by adding aqua ammonia to a s7lution of the double sulp!iocyatiide of mercury and animoniuin. 30. H g (C,H,O,),. zNHy.H,O. €Ig(C,H,O,), Z S H , ~ $. H,O. Hirzel' obtained a compound of the former formula by dissolving mercuric oxide in ammonium acetate and allowing the solution to crystallize. By the same method Balestra" obtained a product to which he gave the formula, KHg,C,H,O, 3NH,C,H,O,. H,O, thus representing the compound as contaiiiing half a molecule of water less than found by Hirzel. I t is soluble in little water but, according to Balestra, is converted by an excess into the product, Hg,NC,H:,O, ($3 1. 31. HgCr,O;.aNH:,. $H,O. Hensgeu'' obtained this compound in the form of golden yellow needles by dissolving mercuric oxide in a solution of ammonium dichromate and allowing the solution to crystallize, ARI MONO 23 AS I C 31E K C UR I C SALTS

.

Just as the normal chloride of mercury with ammonia of crystallization is ammonolyzed by the action of water or of aqua ammonia, giving rise to the formation of aminonobasic products, so it will be clear from the descriptions of the methods by which the many mercuric nitrogen cornpounds enumerated in the following pages have been prepared, that the J. Chetn. SOC.60, 269.

* G-K : S25. G-K : loc. cit. Jsb. Chem. 1890,631. Ley, i n Abegg's Handb. anorg. Chem. with two molecules of water instead of four. Ann. 179,225. J. pr. Chem. 138, 62. * Jsb. Chem. 1851,437; 1852,421. Ibid. 1892,SIS. lo Ibid. 1886,478.

2.2, 676,

wrongly gives this formula


51

principles elucidated above likewise apply to them. T h e presence of solutions of ammonium saIts in contact with the various ammonobasic precipitates tends to convert them into less basic products, even into the normal salts in case the concentration of the ammonium salts is great enough, while the action of water, aqua ammonia or potassium hydroxide always has the effect of rendering the precipitate more basic. I n the following table, which includes all the ammonobasic mercuric salts which have been found described in the literature, is given in the first co1u:nn thz empirical foraulas, in the second column formulas representing the compounds as basic mixtures after the manner ordinarily employed in formulating the more familiar hydrobasic salts, while in the third c d u m n the attempt is made to give the constitutional formulas. TABLE 111. I. 32.

33. 34. 35. 36. 37. 38. 39. 40. 41. 42. 43. 44. 45. 46. 47. 48.

Hg,N,H,CI, HgNH,Cl Hg,NCl Hg,NHCI, Hg,NH,CI3 HgJ,CI, Hg,NH,Cl, HgNH,Br Hg8N,HzOBr9 Hg,NBr HgbNzBr, HgNH,I HgzNI HgNH,Fl Hg,N.N03 Hg,N.NO, Hg,N. C, H,Oz

11.

3HgClz.Hg(NH,),.4NH3 HgCI,.Hg(NH, ), HgC12'Hg3N2 HgCl,.HgNH 3HgC1,. Hg ( N H2 1 2 2HgC1,. Hg3N, zHgCI,NH,Cl HgBr,. H g ( NH,),

111.

HgC12.2NH3.NHZHg-C1 NH2-Hg-Cl Hg:N-Hg-Cl (Cl-Hg),NH HgClz.NH2-Hg-CI (Cl-Hg), : N-Hg-N:(Hg-CI),

NH,-Hg-Br HgBr,zNH3.7NH,-Hg-Br HgBr2.Hg3N2 H g : N-Hg-Br nHgBr2.Hg3N2 (BrHg), : N-Hg-N : ( H g B r ) , H g h . H g ( 2" )2 NHz-Hg-I Hg12Hg3N2 H g : N-Hg-I HgFI,.Hg(NH,), NH,-Hg-FI Hg(N O ~ ) Z . H ~ ~ X ~ H g : N-Hg-NO, H g : N-Hg-NO, Hg (NO, ) 2 . Hg,N, H ~ ( C , H ~ O I ) Z . H ~ ~ N ZH g : N-Hg-C,H302

32. Hg,N3H8C13. According to Hirzel' a compound of this composition is formed by the action of a solution of Alembroth salt on an excess of aqua ammonia. T h e product was obviously an equimolecular mixture of the fusible and infusible white precipitates. 33. HgNH,CI. This is the long knowu and thoroughly identified infusible white precipitate. I t s preparation and properties have already been discussed. 34. Hg,NCI. This ammonobasic salt, known as dimercuriammonium chloride, was first prepared by Weyl, by the action of alcoholic hydrochloric acid on the base, Hg,NOH, ( 3 ) , and by treating the basic chloride, 3HgO.HgCI2, with liquid ammonia. Rammelsberg3 states that the same compound is formed by the dehydration of the chloride of Millon's

Jsh. Chem. 1853, 381. G-K : $34. J. pr. Chem. 146,562.

52


base ( 5 9 ) at 200' and Andre' considered that he had proved its presence in certain mixtures formed by the interaction of mercuric chloride, potassium hydroxide and ammonium chloride in aqueous solution. Hofmann and Marburg', on the other hand were unable to obtain this compound by the actioii of ethereal hydrochloric acid on Hg,KOH; and they furthermore insist that the chloride of Rlillon's base can not be dehydrated without decompo~ition.~ 3j . Ilg,NHCl,. Balestra' obtained a product of this composition by the action of aqua ammonia on an excess of boiling mercuric chloride solution and assigned the formula, Hg,KCl.HCl. In disagreement with the results of Balestra, Millon earlier obtained a product of the composition, Hg,N,H,O,Cl,, (56) by the action of ammonia on ail excess of hot mercuric chloride solution. In case a definite compound of this composition exists it niay be given tlie formula, ClHgNHHgCl, which represents it as a deammoniated product of the infusible white precipitate. 36. Hg,NH,Cl,." Millou6 and Balestra' report the preparation of a compound of this composition by the gradual addition of ammonia to a large excess of a cold solution of mercuric chloride. Balestra gives this conipound the formula Hg,NCl. 2IIC1, and assumes erroneously t h a t he has proved its constitution when he finds that i n accordance with Pesci's reaction' two molecules of ammonia are set free when it is treated with an excess of ammoilium bromide, and that hydrogen sulphide acts upon it to liberate two molecules of hydrochloric acid. Hofinann arid hlarburg9 h a r e shown that Pesci's reaction is of no significance whatever ill proving the presence of the diniercuriamniotlium radical in a compound. I t also appears that the liberation of hydrochloric acid by the action of hydrogen sulphide no more proves tlie constitution of this compound to be Hg2KC1.2HC1than does the liberation of hydriodic acid by the action of Conipt. rend. 108, 1108 ant1 1164. A n n . 305, 209; 2. anorg. Clieni. 23, 12s. :j The writer has attenipted to determine whether this conipound niay be prepared from XiII,HgCl and from HOHgKHHgCl by prolonged washing with liquid aninioiiia on the hypothesis that the former compound niay undergo ammonolysis and that tlie latter may lose water as the result of the mass action of the ammonia. T h e nfusible white precipitate was found to give off ammonium chloride and both conipounds yielded products somewhat richer in mercury than the original compounds, ibut in neither case did the washed salt give analytical results corresponding to the compouiid Hg,NCl. Further work along this line was arrested for the time being by the demoralization of our laboratory resulting from the recent earthquake. Jsb. Cheiii. 1891,586. 15'atts' Dictionary, 3 , 208-209, ( 1 8 9 2 1 , is in error in stating that Millon prepared this compound by heating the infusible white precipitate slowly to 340'. G-I( : S37. Jsb. Chem. 1891,j84. " J . Cheni. SOC.58, 1213. .Inn. 305, 205; Z. anorg. Chetn. 23, 133. Cf. however Pesci: Ibid. 21, 373.

'

ON THE MERCrRY NITROGEN COMPOUNDS

53

hydrogen sulphide on the basic iodide of lead, PbOPbI,.E,O, for example, prove the constitution of this compound to be 2PbO.zHI. 37. Hg,N,Cl,. Mitscherlich’ obtaiued this compound in the form of small, red, crystalline aggregates by heating the infusible white precipitate. Ray’ gives the formula, 2Hg,NCI.HgCl2, to a product approximating Millon’s compound in composition which h e obtained by the action of potassium hydroxide upon a dilute solution of the following double salt. 38. Hg,NH,CI,. This compound was prepared by Ray3 by dissolv i n g his basic nitrite (86), in hydrochloric acid and evaporating nearly to dryness. Pesci’s theory that all the mercury nitrogen compounds are to be formulated as dimercuriammoniuni derivatives, while obviously leading Balestra far afield when he formulates his two compounds Hg,NHCl,, (35), and Hg,MH,Cl,, (36), as Hg,NCl.HCl and Hg2NC1.2HC1, respectively, reaches a climax of uselessness when Ray4 is thereby induced to forrnulate a new double salt, zHgCI,.NH,Cl, as a compound of dimercuriammonium chloride with four molecules of hydrochloric acid, Hg2NC1.4HC1. 39, HgNH,Br. 40. Hg,N,H,,Br,. A compound of the former formula, the bromine analogue of the infusible white precipitate, was first prepared by Mitscherlich’ by the action of aqua ammonia on a solution of mercuric: bromide. More recently, however, Pesci,6 in his attempts to prepare the same compound, obtained instead a product to which lie gave the formula, qHg,NBr.gNH,Br. I t seems not improbable that Pesci’s preparation was a mixture as indicated in the table above. 41. Hg,NBr. Pesci‘ prepared this compound by the action of boiling water or of a dilute potassium hydroxide solution on the compound above (39) as well as by the action of dilute hydrobromic acid on Millon’s base, Hofmann and Marburg8 were unable to obtain such a compound, either by the action of aqua ammonia on a solution of mercuric bromide, by the dehydration of the bromide of Millon’s base, or by the action of dilute hydrobromic acid on Millon’s base. However, there can be no doubt of its existence, for, in addition to the evidence given by the writer in a former paper,’ Mr. F. F. Fitzgerald, woi-king in this laboraG-K : 834 J. Chem. SOC. 81,649. :’Ibid. 8 1 , 648. Proc. Chem. SOC. 1 7 , 96; 18, S6; Damnier : Handb. anorg. Chem. 1903, 4, 631. Abegg : Handb. anorg. Chem. 2 . 2 , 677. G-K : 832. Jsb. Cherri. 1890,628. ’i Ibid, 1890, 628; 2. anorg. Chem. 21, 372. Ann. 305, 213; 2. anorg. Chem. 23, 128. This Journal, 27, 840.

54


tory, has recently obtained a product giving excellent analytical results. 42. Hg5N2Br4. Mitscherlich' obtained this compound by heating NH,HgBr (39) to 340'. Remarking that "the compound is not easy to get," RAY' finds that a product of this composition is forined by the action of potassium hydroxide on an excess of a solution of his double bromide, 2HgBr,. NH,Br. 43. HgNH,I. FrancoisJ obtained this, the iodine analogue of the infusible white precipitate, by the action of concentrated aqueous ammonia, added slowly and at long intervals, upon the ammoniated mercuric iodide, Hg12.2NH3. It was thus obtained as a white, microcrystalline powder, According to Francois large quantities of aqua ammonia added at once give the brown compound, Hg,NI. Francois showed the reaction HgI2.2NH,+XH,HgI I," to be a reversible one and that in aqueous ammonia of 0,923 specific gravity at 21' the concentration of ammonium iodide at equilibrium was 0 . 0 2 0 to 0.023 normal. 44. Hg,NI. This compound was first prepared by the action of liquid ammonia on the basic iodide, 3HgO.HgI2.' More recently Fransois' has prepared the same compound by the action of aqua ammonia on mercuric iodide, and by the action of potassium hydroxide on Hg1,.2NH3. T h e writer has shown' that this arnmonobasic salt is formed by the animonolytic action of liquid ammonia on mercuric iodide as well as by the action of potassium amide on a n excess of mercuric iodide in solution in liquid ammonia. 4 j . HgNH,F. T h e fluorine analogue of the infusible white precipitate has recently been prepared as a light yellow, amorphous powder by adding concentrated aqueous ammonia and then alcohol to a solution of mercuric fluoride,' 46. Hg,X.NO,. This amnionobasic nitrate has been prepared by Pesci' and by Hofnianri and Marburgg by the action of a slight excess of ammonia on an aqueous solution of mercuric nitrate. Tesci" obtained it also by washing the compound, Hg(N0,),.2NH3(zG), with hot water. RBy" was unable to obtain the anhydrous compound,

+

1 G-K : 8 3 2 . Watts' Dictionary, 3 , 209, ( ~ S g o )erroneously , gives Hg,XBr, a s t h e compound formed. I. Chem. SOC.81,649. Conipt. rend. 130, IOZZ. G-K : S29. 5 Compt. rend. 1 3 0 , 571. 6 This Journal, 2 7 . 8 3 8 . 7 Bohm : 2. anorg. Chem. 43, 3 3 2 . F J . Chem. SOC.60, 268; 2 . 2. anorg. Chem. 2 1 , 372. Z. anorg. Chem. 23, 131. l o Jsh. Chem. 1890,630. l1 Z. anorg. Chem. 33, 209.

ON T H E MERCURY NITROGEN COMPOUNDS

55

47. Hg,N.NO,. RBy' reports the preparation of a compound of this composition by the action of ammonia on a solution of mercuric nitrite. His analyses, however, show the presence of some water in his preparation. (Cf 86). 48. Hg,N.C,H,O,. . By digesting the yellow oxide of mercury with a solution of ammoiiium acetate, and by the action of water on the compound H g ( C,H,O,). 2NH,.H,O, ( 3 0 ) , Balestra' obtained this ammonobasic acetale in the form of an amorphous white powder. NIXED HYDROBASIC-AMMONOBASIC MERCURIC SALTS.

Both the oxygen and halogen salts of mercury give with ammonia in the presence of large quantities of water or of dilute alkaline hydroxides representatives of this class of compounds, the result of simultaneous ammonolysis and hydrolysis. Certain of them have also been prepared by the action of dilute acids on the mixed hydro ammono bases, on the carbonates of Millon's base, by double decomposition, and by the action of ammonium salt solutions, not too concentrated, on mercuric oxide. They are variously known in the literature as salts of Millon's base, as oxymercuriammonium salts, as hydrated dimercuriammonium salts, and as hydrated mixed salts of diniercuriammonium with ammonium salts, or with mercuric salts, or with both ammonium salts and mercuric salts. With certain exceptions the members of the group have been obtained as amorphous powders varying in color from pure white, through light shades of yellow, to pure yellow. T h e iodide is brown. They are insoluble in water and in liquid ammonia and in mixtures of these two solvents, but dissolve readily in dilute hydrochloric acid and in solutions of ammonium salts. They are decomposed by the action of potassium iodide or by potassium sulphide and are rendered more basic by the action of dilute potassium hydroxide. Concentrated hot caustic alkalies effect their decomposition with evolution of ammonia. THE HALOGEN SALTS.

I n the table are included all the preparations which have been found described in the literature, arranged in the order of their basicity. In the first column is given the purely empirical formula, in the second the members are formulated as basic mixtures containing, as the case may be, two or more of the known compounds, HgCI,, NH,HgCl, H O H g N H H g C l , HgNHgCl and HgO. I t seems safe to assume that investigation will prove many of these products to be mixtures. J. Cheni. SOC.81,647.

* Ibid. 64, 304.

56


TABLE IY. I.

11.

49. Hg,X:,H,OCI, 50. Hg&‘.;,H,,OC1, j r . HgjS,H,OCI, 52. Hg,,,N,H,OCl, 53. Hg,N3H,,OCI:, 54. HgyS,H,OC1, 5 5 . Hg6N,HtiOCl, 56. Hg5N,,EI,,0,C13 57. H g i SH,O,,Cl~~ j5. H , u , N , H ~ O C I ~ 59. Hg,NH,OCl 60. Hg,N,H,OCI, 6r. Hg6S,,H,0,CI, 62. Hg,S,H,O.,CI, 6;. Hg3SII,0,C1 64. Hg,NH,OBr 6j. Hg,NH,O,Rr 66. Hg,S,H,OBr, 67. Hg,SH,OI 68. Hg,SH,OCN 69. Hg,?:H:,OFl,

( HgCI,.HgO ). 2NH2HgC1 4NH,HgCl. H O H g S H H g C l ( HgC1,. H g O ) .SH,HgCI. Hg,SC1 or HgjN,C1,. H,O 2HgC1, . H O H ~ N H H ~ C I . J H ~ , SorCHg,S,Cl,. I %H,O 2SH2HgC1.HOHgSHHgC1 NH,HgCI. HOHgSI-IHgC1 2SH,IlgC1. HOHgXI1HgCl.Hg,NCI. SH,HgCl.nHOHgSHHgCI (3~g0.11gc1, ) . S H p g c i SH,HgCI.HOHgSHHgC1.2Hg,SC1 HOHgNHIlgC1 or SH,IIgCI. HgO HOHgNHHgCl.Hg,SCl zHOHgSHHgCI.Hg,SCl 2HOEIgNHHgCI.HgO HOHgTHIIgC1.HgO H O H g S I1 €1g Rr I1 0 H fi S H Hg Br. H,O HOHgSHHgI3r. Hg,SBr HOHgSHHgI H O Hg N H IIg C S (FlHg),SH.H,O

49. Hg,N,H,OCI,, and 5 7 . Hg,SH,O,CI,. These basic mixtures were prepared by Thiimmel,’ by the action of ammoniacal solutions of ammonium carbonate and hydrogen sodium carbonate, respectively, on solutions of mercuric chloride. Both products are undoubtedly mixtures, the one formed by nieans of the sodium carbonate being the more basic. I t will be noted that the former compound approxiniates the ammonobasic chloride ( 3 5 ) , in composition ; it is therefore possible that, in this preparation, Thiimmel had ai: imperfectly dried specimen of Hg,NHCl, in his hands. 50. Hg,N,H,,OCI,. Millon’ obtained a product of this composition by adding a boiling solution of niercuric chloride to a large excess of aqua ammonia, followed by thorough washirig of the precipitate withcold water. By following Nillon’s directions, Balestra3 found that the infusible white precipitate is formed, which gradually becomes yellow as it is repeatedly washed, to give finally the chloride of Millon’s base ( 5 9 ) . As indicated in the table, hlillon’s product was probably a specimen of the infusible white precipitate, partially changed into the chloride of Millon’s base. 51. Hg,h’,H,OCl,. Balestra obtained a product of this composition, to which he gave the formula, ~Hg,NCl.HgCI,.H,O,by washing the compound, Hg,NH,CI, ( 3 6 ) , withcold water. This product may be formulated as au imperfectly dried specimen of the compound, Hg,N,CI, (37). Jsb. Chern. 1887,579. G-R : 83:. Jsb. Cheiri. 1891, j84.

Ibid.

1891,

555.


57

52. Hg,,N,H,OCl,. Balestra found the preceding preparation to lose one-half a molecule of water a t I 1 0 - 1 15’, which leads to a product still more closely approximating in composition the compound, Hg,N,CI,. 56. Hg,N,H,O,CI,. Millon prepared this product by thoroughly washing the compound, Hg,NH,CI, (36), with cold water, and also by adding aqua ammonia slowly to a large excessof boiling mercuric chloride solution. Following Millon’s first method, just mentioned, Balestra’ was unable to prepare the same compound, but obtained instead, Hg,N,H,OC1, (5 1). Following Millon’s second method, he obtained the compound, Hg,l\;HCI, (35). 59. Hg,NH,OCl. This well characterized compound, the chloride of Millon’s base,’ has been prepared by a number of investigators, especially by the action of water or dilute potassium hydroxide solution on the white precipitates. I t is also formed by the action of dilute hydrochloric acid, or of ammonium chloride, on Millon’s base, and in general by the action of water or dilute potassium hydroxide solution on any of the less basic chlorides listed in this or the preceding section, or by the action of ammonium chloride on any of the more basic compounds. An interesting method of formation is that of the actioii of ammonium chloride on an aqueous solution of mercuric acetaniidee4 60. Hg,N,H,OCl,. Although, according to Hofmann and Marburg,, the chloride of Millon’s base does not lose water without complete decomposition, a product of the above composition has nevertheless been prepared.‘ 62. Hg,N:H,O,Cl,. 63. Hg,NH,O,Cl. Schmieder obtained the former of these products by dissolving the compound, HgSO,. 2NH,. H,O (28), in dilute hydrochloric acid, and pouring the solution into a slight excess of potassium hydroxide solution. H e obtained the latter compound by boiling the former with a concentrated solution of potassium hydroxide. Since, according to Schmieder, continued boiling of the latter compound with potassium hydroxide gives finally mercuric oxide, it seems fair to conclude that both of the above preparations were nothing more than mixtures of the chloride of Millon’s base with mercuric oxide. I n addition to the prepiration ( 6 0 ) , which had previously been described -by others, Andre* obtained also the basic mixtures (53), (54), ( 5 5 ) , (58) and (61), by the interaction of ammonia and mercuricchloride, G-K 837. Jsb. Chem. 1891,585. G-K : 837. E’urth : Monatsh. 23, I 155. Ann. 3 0 5 , 213. Andre : Conipt. rend. 108, 1110and 1165; Ray : J. Chem. SOC.81,648; Sen: Z. anorg. Chem. 33, 206. G-K : 838. Compt. rend. 108,233, 290, 1108 and 1164.

58


in some cases with, in others without the introduction of potassium liydroxide into the reaction mixture. I n view of the fact that a t least some of Andr@'s preparations have been assumed to be chemical individuals,' it may be pointed out that the conditions under which he worked were ideal for the formation of basic mixtures, and that, in all probability, his preparations mere not compounds a t all, but were mixtures which happened to approximate molecular proportions. Millon was well aware of the danger of reporting mixtures of the mercury nitrogen compounds as chemical individuals. H e tells us in one place' that by pouring ammonia into solutions of mercuric chloride lie obtained precipitates containing an amount of mercury varying from 75.5 to 84.7 per cent. depending upon the temperature of the mercuric chloride solution and the extent to which the washing was carried. 64. Hg,NH,OBr. 65. Hg,KH,O,Br. 66. Hg,N,H,OBr,. Hofmann and Marburg" prepared the bromide of Millon's base corresponding to the first of the preceding formulas by the action of dilute liydrobroniic acid on Millon's base, while by the action of ammonia on a solution of mercuric bromide, which presumably should give the same coinpound, they obtained a product of the second formula. RAY' has obtained a bromide cor res poi] ding to t h e third for in u la, 67. Hg,NH,OI. This compound, Nessler's precipitate, has frequently been the subject of investigation." It is formed by the action of aqua ammonia on mercuric iodide and in general when mercuric iodide and ammonia are brought together in alkaline solution. According to Franqois' the anhydrous compound, Hg,NI, alone, exists. 68. Hg,NH,OCX. 'I'he cyanide of Millon's base has been obtained by Hofmaun and Marburg,8 in the form of brilliant yellow crystals, by the action of alcoholic ammonia oil mercuric cyanide. 69. Hg,SH,OF,.!' Finkener'" has obtained an amorphous powder of this composition by the action of ammonia on a solution of mercuric fluoride. T h e compound may be formulated as a hydrated ammonobasic fluoride, Hg,NHF,.H,O, or as a mixture of Bohm's compound, NH,HgF, with the hydrobasic salts, HOHgF, as indicated in the table above. Watts' Dict. Chem. 3 , 208. (1S92) .4nn. chim. phys. (31 1 8 , 421. Ann. 305, 212. Z. anorg. Cheni. 23, 129. j J. Chem. SOC. 8 1 , 649. G-K : Sz9. Compt. rend. 1 3 0 , 571. %. anorg. Chem. 23, 130. Ley, in h b e g g ' s Handbuch der anorganischen Chemie, gives the f o r m u l a , OHg,NH,F. I" G-K : 843.

'

2.2,

6;6, erroneously

O N T H E MERCURY NITROGEN COMPOUNDS

59

NITRATES.

T h e following basic nitrates have been found described in the literature. T h e empirical formulas are given in the first column. In the second column they are given as basic mixtures after the manner used in formulating the chlorides above, notwithstanding the fact that the nitrate, NH,HgNO,, corresponding to the infusible white precipitate has never been prepared, TABLE V. I.

70. 71 * 72. 73. 74. 75. 76. 77.

Hg,N,Hl,0.3N0, HgzNsHi,02. 3x0, Hg,N2H,0.2N0,. Hg3NzH,0.2N0, H~QN,H,.~NO:< Hg,SH,O.NO, Hg,N,H,O. 2N0, Hg,KH,O,.NO,

11.

Hg( NO,),.zNH,.H,O.KH,HgNO, Hg(KO,) ,.ISH,. 2 H , 0 . N H 2 H g N 0 , ?r;H,HgNO,. %H,O or Hg(NO,),.zNH,HgO NH,HgNO,. HOHgNHHgNO, H g (N 0 , ) 2 . 4 H g 0 . z H g 2 N N 0 , HOHgNHHgNO, HOHgNHHgNO,.Hg,NNOB HOHgNHHgNO,.HgO

7 I. Hg,N,H,,O,. 3NO,.I This compound, known as Kane's salt, was first prepared by dissolving Soubeiran's salt, ( 7 5 ) ' or mercuric oxide in a boiling solution of ammonium nitrate and allowing the solution to cool, when the salt crystallizes out in the form of small brilliant needles. Pesci, has confirmed the existence of this salt and finds that when heated to I 1o'-115O, it loses one molecule of water to give a product of the composition of (70) in the table above. 72. HgzN,H,0.2NO,. This compound has been prepared by dissolving Mitscherlich's salt,' (73) or Soubeiran,s salt,5 (75), in a solution of ammonium nitrate and evaporating the solution when a compound of the above composition crystallizes out; and also by evaporating to crystallization the solution formed by adding ammonia or ammonium carbonate to a solution of mercuric nitrate until the precipitate at first formed is redissolved.' Pesci obtained the same compound by supersaturating a dilute solution of mercuric nitrate with ammonia, a process similar to that which previously had given Pagenstecher the more basic product, Hg,NH,O,.NO,, ( 7 7 ) , and gave it the formula, Hg,NNO,.NH,NO,.H,O. This compound is especially interesting for the reason that it approximates in composition the nitric acid analogue of the infusible white precipitate as indicated in the table above. Fehling, Handworterb. Chem. ( 1 8 p ) , 5, 1099, describes a compound, NHg,NO,.zNH,NO,, which can be none other than Kane's salt in the formulation of which t h e water has been omitted. Kane : Ann. chim. phys. 72, 248; G-K : 848. Jsb. Chem. 1890,630. ' G-K : 847. Kane : Ann. chim. phys. 72, 248. J. Chem. Soc. 6 0 , 268.

60

E D W A R D C. F R A X K L I X

73. Hg3N,H,.20X0,, Hg,S,Hc,0,.2X0,, or Hg,X,H2.2S:,.0 This SOcalled Mitscherlich's salt is obtained a s a white, delicate precipitate by treating dilute, barely acid mercuric nitrate solution, with dilute aqueous ammonia not in excess, and by boiling the basic nitrate, H g ( S0,,),.2HgO, with a solutiori of ammonium nitrate.' Pesci fourid that this compound is also formed by the action of cold wateron thesalt Hg(SO:I)1.2NH:, (26). Fehlitig* describes a compound QHg.LSSO,,,.SE~,SO,:, which call be none other than Mitscherlich's salt in the formulation of which the water has been omitted. 74. Hg,N,O,.@O,;. This complex, to which the formtila, 2 [SHg( HgOHg)OHgNO,] .Hg(XO:J,. has been given was prepared b y Hirzel:' by thoroughly triturating freshly precipitated mercuric oxide with a moderately concentrated solution of aninioriiuni nitrate, followed by washing of the residue with hot water. T h e ponder thus obtained n-as obviously a mixture. I n any event Pesci' was unable to prepare such a compound but obtained instead the compound (&+6 j. /3. Hg,SH,O.SO:,. T h e nitrate of Millon's base, knon.n also a s Soubeiraii's salt, has been prepared by the action of slight excess of animonia on a dilute solution of mercuric nitrate,' by the action of boiling water on Mitscherlich's salt,ti j 7 3 ) , and by the action of water on Kane's salt,' (71). More recently Fiirth' has prepared this compound by the action of ammonium nitrate on a solution of mercury acetamide. By the action of water on certain of the basic nitrates here given, Pesci has obtained a product which he calls diinercurianimoniiini nitrate. H e is so thoroughly couvinced that the compound, Hg,XXO.), is n neverfailing constituent of these nitrates that he apparently refers to Ilg,KSO, and H O H g N H H g K O , indifferently as dimercuriamnionium nitrate. I t is not possible from a study of the abstracts of his papers to know always to which compound he refers. 76. Hg,S,H,O. 2x0:;. Kay!' obtained a compound of this coinposition by treating his diniercurianinioni~i~~~ nitrite (47) with nitric acid. 77. Hg,SH,O,.KO:,. Pagenstecher obtained this con1pound. knoxvn as dioxytrimercuriammoniunl nitrate, by treatitig a concentrated solution of mercuric nitrate with a large excess of ammonia. Pagenstecher probably had a mixture in his hands.

--

G-K : 546: I'esci : J . Clieni. SOC. 60, 26s. €IandwOrterb. Chein. rSyo) 5 , royy. :I G-K : q i , Jsb. Chern. 1890, 630; Z. aiiorg. Cherri. 21, 3 7 2 . G-I( : Sj6. fi A n n . chim. phys. 72, j49. ' Jlonatsli. 23, 1156. ,y %. anorg. Chein. 3 3 , 2 0 9 . G-K : 8~16.

'

ON THE MERCURY N I T R O G E N COMPOUNDS

61

SULPHATES.

TABLE VI. 11.

I.

is. Hg20S;18H,44016. 19Sd4IS( HgS0,.2NH,). rgH,O.EIgO 79. Hg,S,H,O.SO+ Hg,,N,H60,.S0, 81. Hg,K+H2.2SO, 82. HgjN,H,0,.2SO, 83. Hg,N,H,O.SO, 84. Hg,N,H,O,.SO+ 85. Hg5S,H,0s. SO4 SO.

HgSO+.2NH:,.HgO.or (XH,Hg),SO,.H,O ~ g S 0 , . 2 N H , . 2 H g 0 or XH,Hg-SO,-HgNHHgOH.H,O (NH,Hg),S0+.3( Hg,N)nSO, (NH,Hg),S0,.3( HOHgXHHg.),SO,

(HOHgNHHg),SO,.(Hg,K),SO, (HOHgNHHg),SO, (HOHgNHHg),SO,.HgO.

78. Hg,,,X~isH14,0,6, 1gS0,. By saturating concentrated aqua ammonia with mercuric sulphate, adding an equal volume of aqua ammonia saturated at oo, and allowing the solution to stand for twenty-four hours, Pesci' obtained a crop of well formed, prismatic crystals which gave analytical data leading to the above complex formula. Pesci gave his product thevery unlikely formula, 5 ( Hg,N),SO,. I ~ ( N H , ) , S O , 16H,o. . The crystals lose water readily on exposure to the air, and are converted into the sulphate of Millon's base, (84) by the action of cold water. As indicated in the table above, Pesci's product was, in all probability a partially dehydrated, slightly basic specimen of the compound HgSO,. 2NH,. H,O, (28). 79. Hg,N,H,O SO,, 80. Hg,N,H,O,.SO,, Millon' prepared these two complexes, together with the compound, HgSO,.2NH, ( 2 7 ) , all in the form of large prismatic crystals, by dissolving mercuric sulphate in concentrated aqua ammonia to saturation, and evaporating the solution in an atmosphere of ammonia. Following Millon's directions, Pest? was unable to obtain either of these basic sulphates, but obtained instead, the sulphate of Millon's base or ammonia turpith (84). 82. Hg;N,H,O:,. 2S0,. Schmieder' obtained a product of this composition by the action of cold water on HgS0,.2NH,.H20, (28), and by pouring a solution of ammonium sulphate saturated with mercuric oxide into much cold water. H e found that boiling water removes ammonium sulphate, and that boiling potassium hydroxide solution gradually converts the compound into mercuric oxide. Schmieder found also that his compound is reconverted into HgS04.2NH,.H,0 by the action of concentrated ammonium sulphate solution. Following Schniieder's directions, Pesci' obtained a compound of the same composition, which he found to be converted into ammonia turpith, ( S q ) , by the action of boiling water, and which contrary to Jorgensen,, loses three molecules of

' Jsb. Chem.

1890,631. G-K : 825. J. Chem. SOC.60, 269. G-K : 826. J. Chem. SOC. 60, 269. G-K : 824.

62

E D W A R D C. FRANKLIN

water when heated to I I j”,to give a compound of the composition, Hg,N,H,.aSO+, ( 8 1 ) in the table above. 84. Hg,S,H,O,.SO,. 83. Hg,N,H,O.SO,. Ammonia turpith, or the S U ~ phateof Millon’s base is the most thoroughly established of the mixed hydrobasic-ammonobasic sulphates of mercury. Jorgenseii’ gives the result of analyses by Kane, Millon, Hirzel and Schmieder which agree closely with the first of the above formulas. T h e compound is formed by the action of aqua ammonia on a solution of mercuric sulphate ; b y dissolving mercuric sulphate it1 concentrated aqua ammonia and diluting with water ; by the action of a solution of ammoniuni sulphate on mercuric oxide or on the basic sulphate of mercury, HgSO,.zHgO ; by the action of boiling water on HgSO,.aSH,.H,O ; and by the action of dilute sulphuric acid 011 Mil1011’s base, or on the hydro amnion0 base, H g : N-Hg-OH ; all of which methods are in strict accordance with the theory outlined elsewhere in this paper for the formation of mixed hydrobasic-ammonobasic salts. I t has most frequently been obtained as a white or yellowish dense powder, occasionally as a crystalline crust. P e d obtained it in the form of octahedral crystals. According to Schmieder, aniiiionia turpith does not lose water at I 1 5 ~ . Abegg,‘ and Dammer,5 in their respective dictionaries, erroneously describe ammonia turpith under the second of the above formulas. RAy6 also uses this formula but gives no analytical data supporting it. 85. Hg,N,H,O,.SO,. Schmieder’ prepared this compound by dissolving HgSO,.zNH,.H,O ( 2 8 ) in dilute sulphuric acid, pouring the solution into an excess of a dilute solutioti of potassium hydroxide and washing the precipitate with warm water. Following Schmieder’s directions Pest? failed to get this compound but obtained ammonia turpith, (84) , instead. MISCELLANEOUS SALTS

In addition to the halogen salts, the nitrates and sulphates given in the tables above, a considerable number of other salts found described in the literature are listed together in TABLE VII. I.

11.

86. Hg,N2H,0.2N0, HOHgNHHgNO,. Hg,NNO, 87. Hg,NH,O.NO, HOHgNHHgKO, 88. Hg,NH,O.BrO, HOHgNHHgBrO, G-K : 824. J. Chem. SOC.60, 269. G-K : S24. Handb. anorg. Cheni. 2.2, 677. I, Ibid. 2 . 2 , 906. Proc. Cheni. Soc. 2 0 , 250. G-K : 827. J. Chem. SOC.60. 269.

’ ‘


63

TABLE VII. Continued. I.

89. HgZN3H100 * 3I OS go. Hg,N,H,,O,. 210, 91. Hg,N,H,O,.CrO, 92. Hg8N,H40,.4Cr0,.

93. Hg4NzH,O,.SeO, 94. Hg,N,H,O,.ZSOa 95. Hg4N,H40vCO~ 96. Hg8N,Hlo0,.2C0, 979 Hg4N2H603*C0,* 98. Hg,N,H,O,.C,O, 99. Hg,NH,.PO, 100. Hg,XH,O.PO, 101. Hg,,NjH,,0,,.P04. 102. Hg:,NH,.AsO, 103. Hg8N,H,,0.3C,H,0, 104. Hg,K,H,,05.2C4H,0, 10j. Hg,N,H, 03. C4H,0, 106. Hg,N,H,,.7C,Hj0, 107. Hg,NH40,.C,Hs0, 108. Hg,NH,O.SCN

11.

H g ( IO,)2.2NH,.H,O.SH,HgIO3 NH,HgIO,. 2HgO.NH,. %H,O (HOHgNHHg),CrO, 3HgCr0,. HgO. (HOHgNHHg),CrO, (HOHgNHHg),SeO, (HgS0,.2HgO). (NH,Hg),SO, or HgSO;,. (HOHgNHHg),SO, ( HOHgKHHg),CO, (HOHgNHHg),CO,. %H,O (HOHgNHHg),C03.H,0 ( HOHgNHHg),C,04 H g : PO,-Hg-NH, H g : PO,-Hg-NH-Hg-OH Hg2NH,P0,.4( IHgO.NH,.H,O) EIg : AsO,-Hg-NH, 2 t ”zHg )zC~HIOG. (HgzK )zC~H,OB.HZO (HOHgNHHg),C,H,O,.~H,O NH2Hg-C,H4O6-HgNHHgOH. 2H2O 3 [ H g ( C,H,O,),. 2”,I.”,HgC,H,O, HOHgNHHgC,H,O,.H,O HOHgNHHgSCX

86. Hg,N,H,O. aNO,. 87. Hg,NH,O.NO,. Besides the formula, Hg,N. NO,( 47), which RBy assigns to his dimercuriammonium nitrite, he, in other places,’ gives his compound the formula, aHg,NNO,.H,O. Hofmann and Marburg’ state that the formula is Hg,NH,O.NO,, and that the compound does not lose water either over sulphuric acid or when heated to 125’ in a current of ammonia. 88. Hg,NH,O.BrO, or Hg,N,H,O,. 2Br0,. Rammelsberg’ obtained a compound of the former formula as a yellow, bulky powder by the action of ammonia on a solution of mercuric bromate. In a later paper Rammelsberg4 gives the formula 2NHg,BrO3.3H,O. 89. Hg,N,H,,O. 310,, Hg,N3I3,,O,.310,. Hg,N,H,. 310,. Milled prepared a compound of the composition of the first or second formula above by the action of an excess of aqua ammonia on mercuric iodate. By heating mercuric iodate with ammonia Rammelsberg’ obtained a product to which he gave the formula, Hg,NIO,. 2NH,IO,, corresponding to the third of the above formulas. Very probably the compounds of Millon and Rammelsberg were mixtures of mercuric iodate with ammonia of crystallization and the ammonobasic salt, NH,HgIO,, as indicated by the formula, Hg(IO,),. 2NH,.NH,HgIO,.xH,O. Pr. Chem. SOC. 17, 96;and 18,85; 2. anorg. Chem. 33, 194.

Ann. 305, 214. G-K : 833. J. pr. Chem. 146,568. G-K: 832; Ann. chim. phys. ( 3 ) 18, 411. J. pr. Chem. 146, 568.

64

EDWARD C . F K A S K L I N

90. Hg,N,H,,O,. 2 1 0 , . Ranimelsberg’s’ product of this composition, which he prepared by digesting the basic periodate, H g ( 10,),.4HgO, with amnionia, was very probably, a mixture of NH,HgIO, and Ifillon’s base, KH,HgIO,. (zHgO.NH,,.xH,O). 91. Hg,N,H,O,.CrO,. Hirzel’ prepared this compound. the chromate of Millon’s base, as a light yellow amorphous powder, by the action of aqua ammonia on the following compound, ( 9 2 ) . I t has also been prepared by Hemgen:’ by the action of boiling ammonia 01 potassium h.droxide solutioii on the amnioiiiated mercuric dichromate, (31), or by diluting a solution of mercuric cliroinate in ammonium chromate with much water. 9 2 . Hg,N,H,O3.4CrO,. Hirzel’ olitained a dexise, orange-red, basic mixture of this composition by heating mercuric oxide with a solution of am nioni u iii dichromat e. 93. Hg,S,H,O,.SeO,. According to Watts’ Dictionary,” the selenate of hlillon’s base has been prepared by dissolving the basic selenate, HgSeO,. zHgO, in concentrated aqueous ammonia and precipitating by the addition of much water. 94. H ~ , S , H , O , . Z S O , , .Hg,X,H,O.zSO,.’ ~ This basic mixture was prepared by ilirzel by the action of potassium hydroxide on a solution of the double salt, HgSO:,.(NH,),SO:,. g j . Hg,S,H,O,-CO::. 96. H g , S , H , , O , ~ ~ C O , . 9 j . Hg,S,H,iO,,*CO,,. Rammelsberg’ prepared a carbonate of Millon’s base, corresponding to the first of these formulas, by boiling the base with a solution of sodium carbonate. compound corresponding to the secoiid formula was prepared by Millon,!’ by the action of carbon dioxide on a suspension of Millon’s base, and by treating the base with ammonium carbonate or acid potassium carbonate solutions, Hirzel ‘’I obtained the same product by boiling an ammonium carbonate solution in contact with mercuric oxide. A product of the composition represented by the third formula was obtained by Hirzel” by digesting mercuric oxide with anin~oniunicarbonate solution in the cold. Certainly these compounds cannot be essentially different. 98. Hg,T*;,H,O,. C,O,. Millon” obtained this oxalate a s a white pow-

’ J . pr. Chem. 146,569.

Jsb. C h e m . 1852,4 2 1 . Ihid. 1886,475. Ibid. 1852,421. (1S9z)3 , 209. G-K : 823. Dammer : Handb. anorg. Cliem. 2 . 2 , 906 (rS94). r: J. pr. C h e m . 146, 5 6 j . !’ G-K : 819; Ann. chim phys. 18, 533. Io G-K : 819; Jsb. Chem. 1852, 421. l 1 Anii. chim. phys. (3) 18, 409,

:i

‘


65

der by digesting mercuric oxalate with aqua ammonia in excess. T h e same compound was also prepared by Hirzel I by the action of a solution of ammonium oxalate on mercuric oxide. gg. Hg,NH,. PO,. This compound was prepared by RBy' and by him formulated as dimercuriammonium acid phosphate, Hg,NPO,H,. T h e formula given in the table represents it as an ammonobasic salt. Hirze13 obtained a white powder of this com100. Hg,NH,O. PO,. position by the action of a solution of ammonium phosphate on mercuric oxide. 1 0 1 . Hg,,N,H,,O,,.PO,. Rammelsberg' obtained a product to which he gave the formula, (NHg,),PO,. zNHg,OH. 1oH,0, by heating Millon's base with an excess of phosphoric acid. His preparation niay be formulated as a mixture of the compound, Hg,NH,PO,, ( g 8 ) , with unchanged Millon's base as indicated in the preceding table. 102. Hg,NH,AsO,. A compound of this composition was prepared by Hirzel' by the action of a solution of ammonium arsenate upon mercuric oxide. 103. Hg,N,H1,O.3C,H,O,. A product of this composition mas obtained by Balestrafiby diluting an ammonium tartrate solution of mercuric oxide with water. T h e preparation to which Balestra gave the formula, z (Hg,N),C,H,O,. (NH,),C,H,O,.H,O, was in all probability a mixture. 104. Hg,N,H,,06. zC,H,O,. Balestra' prepared this compound, to which he gave the formula, 2 [(NHg,),C,H,O,].~H,O by dissolving mercuric tartrate in aqua ammonia and evaporating the solution over sulphuric acid. T h e preparation was probably an imperfectly dried specimen of tartrate of Millon's base. 105. Hg,N,H,O,. C,H,O,. Hirzel'found that mercuric oxide dissolves for ammonium tartrate giving a thick viscous solution. On evaporation well formed crystals were deposited which, however, he did not succeed in sufficiently freeing from mother liquor for analysis. As is uniformly the case when mercuric salts separate from a solution containing a sufficient concentration of the corresponding ammonium salt, there is formed the normal salt with ammonia of crystallization, so here i n all probability, Hirzel had an ammoniated tartrate in his hands. When the viscous solution was diluted Hirzel obtained a precipitate of the above composition which may be formulated as a hydrated mixture of (NH,Hg),C,H,O, and (HOHgNHHg),C,H,O,. Jsb. Chem. 1852, 421. Fr. Chem. SOC.20, 250. G-K : 820. J. pr. Chem. 146,567. Jsb. Chem. 1852,420. Ibid. 1892,816. 1. c. Jsb. Chem. 1852,422.

66

WILSON H . LOW

106. Hg,N,H,,.7C,H5O8. Balestra’ prepared this compound by dissolving mercuric oxide in ammonium salicylate and evaporating the solution to crystallization. Balestra gave his product the formula, 2Hg,N. C,H,O,. NH,. C,H,O,. More probably, however, it was a somewhat ainmonolyzed specimen of the normal salt as indicated by the formula in Table VII. I t is decomposed by the action of water. 107. Hg,NH,O,.C,H,O,. Hirzel’ obtained a compound of this coniposition by heating the ammoniated mercuric acetate, (30). According to Gerreshein? the acetate of Millon’s base is formed by the action of acetic acid on the base. 108. Hg,NH,O.SCN This sulphocyanide of Millon’s base4 has been prepared by the action of ammoniaon a solution of mercuric sulphocyanide, on a solution of the double potassium mercuric sulphocyanide, and by the action of water on the ammoniated mercuric sulphocyanide, (29). I t forms a yellow amorphous powder. T h e material contained in this paper was collected during the earlier part of the past year, for the purpose of determining whether or not the writer’s theory concerning the constitution of the mercury nitrogen compounds is worthy of further consideration, and to serve as a basis for a thorough experimental review of the whole field. I t was not the original intention to publish, until after a reasonable amount of experimental work had been done, which, it is expected, will eliminate as definite chemical compounds many of the products which have been described in the past. However, as a result of the demoralization of our laboratory by the great earthquake and the consequent impossibility of carrying on much research work in the immediate future, it seenis advisable to print this summary at the present time. Experimental work will be continued as soon as possible, STANFORD c N I V E R S I T Y C A L I F O R N I A , .%I T C M N , 1906

DETERMINATION OF ANTIMONY AND TIN IN BABBITT, TYPE METAL OR OTHER ALLOYS. [APPLICABLE

ALSO WHEREVER THE ANTIMONY AND TIN

A R E OBTAINED AS

SULPHIDES.] BY WILSON H

Received Oct.

Low.

11,

1906.

The accurate determination of antimony and tin in alloys has always been a more or less troublesome operation, and almost all of the published Jsb. Cheni. 1892, S16. Ibid. 1852,421. :$ Ann. 195,375. Philipp: Ibid. 180, 341. Ehrenberg: J. pr. Chem. 138,62.

ON THE MERCURY NITROGEN COMPOUNDS - Journal of the

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