DAVAL-SANTOS, Jude A.

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Page 1 of 17

Separation of the Metals into Analytical Groups (based on Holtzclaw & Robinson scheme and Svehla scheme) Group 1 Cations (Group I Chlorides) Description of the Tests (from USP 30 NF 25) (1) With 2 N sulfuric acid, solutions of lead yield a white precipitate that is Perceptible Result(s) White precipitate (Svehla, 1996, p.64) No dissolution of precipitate; white precipitate persists (Soine & Wilson, 1967, p.515) Principle Involved/ Notes Double displacement precipitation reaction (Holtzclaw & Robinson, 1988, p.945). The sulfate ion is converted largely to HSO4- by H3O+ in high concentration (Holtzclaw & Robinson, 1988, p.962), specifically Pb(HSO4)2 (Gilreath, 1954, p.194, 199). The concentrations may not be weakly acidic not enough to provide enough H 3O+ to form the soluble bisulfate. Pb(II) is essentially basic, although with alkalies Pb(OH) 2 will form plumbites. That is to say it will act like an acid (Parks et al, 1949, p.209). The fact that its hydroxide is amphoteric is an indication of its nonmetallic character. The solubility of lead chloride increases with temperature (Holtzclaw & Robinson, 1988, pp.833, 941). Precipitate dissolves though complex ion formation of tetrahydroxoplumbate(II) (Holtzclaw & Robinson, 1988, p.943). The higher valence state (+4) is primarily acidic but also amphoteric (Parks et al, 1949, p.941). Precipitate dissolves though complex ion formation of tetraacetoplumbate(II). The formation of a weak electrolyte lead acetate (Holtzclaw & Robinson, 1988, p.943). Double displacement precipitation reaction. The solution be free from mineral acids because in acidic media, PbCrO4 will not be formed but the dichromate ion, and the latter yield orange-red aqueous solutions; 2 CrO42- + 2 H+ Cr2O72- + H2O (Svehla, 1996, p.225). CH3COOH is a weak acid thus it could not provide enough H 3O+ to form the dichromate, which could latter form an orange-red aqueous solution (Svehla, 1996, p.225).

Corresponding Equations Pb(NO3)2 + H2 SO4 PbSO4 + 2 HNO3 (Svehla, 1996, p.64) PbSO4 + HCl no reaction (Soine & Wilson, 1967, p.515) PbSO4 + HNO3 no reaction (Soine & Wilson, 1967, p.515) PbSO4 + 2 NaOH Na2 SO4 + Pb(OH)2 (or H2PbO2) Pb(OH)2 + 2 NaOH Na2PbO2 + 2 H2O (Soine & Wilson, 1967, p.515) PbSO4 + 4 NaOH Na2 SO4 + Na2[Pb(OH)4] (Svehla, 1996, p.64) PbSO4 + 4 CH3COONH4 (NH4)2[Pb(CH3COO)4] + (NH4)2SO4 (Svehla, 1996, p.65) PbSO4 + 2 CH3COONH4 Pb(CH3COO)2 + (NH4)2SO4 (Holtzclaw & Robinson, 1988, p.932). Pb(NO3)2 + K2 CrO4 PbCrO4 + 2 KNO3 (Svehla, 1996, p.65)

a. insoluble in 3 N hydrochloric acid or 2 N nitric acid, but is

b. soluble in warm 1 N sodium hydroxide and

Dissolution of precipitate forming a clear, colorless Solution (Svehla, 1996, p.64)

c. in ammonium acetate TS. Lead (II) (2) With potassium chromate TS, solutions of lead salts, free or nearly free from mineral acids, yield a yellow precipitate that is

Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.65)

Bright yellow precipitate (Soine & Wilson, 1967, p.515)

a. insoluble in 6 N acetic acid but it

PbCrO4 + CH3COOH no reaction (Soine & Wilson, 1967, p.515)

No dissolution of precipitate; bright yellow precipitate persists (Soine & Wilson, 1967, p.515)

b. soluble in 1 N sodium hydroxide.

PbCrO4 + 2 NaOH Na2 CrO4 + Pb(OH)2 (or H2PbO2) Pb(OH)2 + 2 NaOH Na2PbO2 + 2 H2O (Soine & Wilson, 1967, p.515) -----------------------------------------------------------PbCrO4 + 4 NaOH Na2 CrO4 + Na2 PbO2 + 2 H2O (Soine & Wilson, 1967, p.515) PbCrO4 + 4 NaOH Na2[Pb(OH)4] + Na2 CrO4 (Svehla, 1996, p.65)

Dissolution of precipitate forming a yellow solution (Lee, 1996, p.728)

Pb(II) is essentially basic, although with alkalies Pb(OH) 2 will form plumbites. That is to say it will act like an acid (Parks et al, 1949, p.209).

Formation of the soluble complex, which suppresses the Pb 2+ ion concentration to such an extent that the solubility product of PbCrO4 is no longer exceeded (Svehla, 1996, p.226)

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General tests: (1) When applied to bright copper foil, solutions of mercury salts, free from an excess of nitric acid, yield a deposit that upon rubbing, becomes bright and silvery in appearance.

Hg (I): Cu + Hg2(NO3)2 Cu(NO3)2 + 2 Hg

Hg (II): Cu + HgCl2 CuCl2 + Hg (Soine & Wilson, 1967, pp.426-7) Hg (I): Hg2(NO3)2 + H2 S HgS + Hg + 2 HNO3 (Soine & Wilson, 1967, pp.424)

Deposit of mercury on a copper foil and then becomes bright and silvery upon rubbing (USP CI, 2006, p.140) Black precipitate (Soine & Wilson, 1967, pp.424) White precipitate, which turns yellow to brown and finally to black (Soine & Wilson, 1967, pp.426)

Single replacement reaction since copper is higher in the electromotive series than Hg (Soine & Wilson, 1967, 672). The solution of Hg should be free from an excess of HNO3 since the Hg2(NO3)2 tend to hydrolyze in aqueous solutions to form basic salts thus stabilizing it but preventing it from reacting Hg2(NO3)2 + H2O Hg(OH)2NO3 + HNO3 (Soine &Wilson, 1967, p.424). Disproportionation reaction (Holtzclaw & Robinson, 1988, p.931). White in the presence of HCl : HgCl2 2 HgS (a complex of the original mercuric salt with mercuric sulfide); yellow (complex having greater proportions of HgS) (Soine & Wilson, 1967, pp.426). When heated, HgS becomes bright red; the red sulfide is isomeric with the black and has in the past has been used as the pigment vermilion (Holtzclaw & Robinson, 1988, p.845). Colorless (NH4)2S; HgS is one of the least soluble precipitates known but soluble in solutions of soluble sulfides in the presence of an excess of hydroxide ions and forms the thiomercurate ion [HgS2]2- (Holtzclaw & Robinson, 1988, p.845). Double displacement reaction. Double displacement reaction. Hg2(OH)2 is very unstable toward heat and light, thus it decomposes (Soine & Wilson, 1967, p.425). Stable dinuclear metal ion (Hg-Hg)2+, bonded using 6s orbitals. The only other metals which form dinuclear ions are (Zn-Zn)2+ and (CdCd)2+ , which are unstable and have only been detected spectroscopically (Lee, 1996, p.846). Double displacement reaction. Calomel : Hg2Cl2 (Holtzclaw & Robinson, 1988, p.842). Decomposition. Corrosive sublimate: HgCl2 (Holtzclaw & Robinson, 1988, p.842). Disproportionation. This reaction can be used to differentiate mercury(I) ions from lead(II) and silver(I). Hg(NH2)Cl is a white precipitate but the finely divided Hg makes it shiny black. The name calomel (Greek = nice black) refers to this characteristic of the originally Hg2Cl2 (Svehla, 1996, p.68). Ammonia water serves as a medium for the auto-redox of Hg2Cl2 (Gilreath, 1954, p.186).

Mercury

(2) With hydrogen sulfide, solutions of mercury compounds yield a black precipitate that is

Hg (II): 3 HgCl2 + 2 H2 S HgCl2 2 HgS + 4 HCl HgCl2 2 HgS + H2 S 3 HgS + 2 HCl (Soine & Wilson, 1967, pp.426)

a. insoluble in ammonium sulfide TS and

HgS + (NH4)2S no reaction (Svehla, 1996, p.78)

Black precipitate (Svehla, 1996, p.78) Dissolution of precipitate forming a solution with rotten egg odor (Holtzclaw & Robinson, 1988, p.667)

b. in boiling 2 N nitric acid.

HgS + HNO3 Hg(NO3)2 + H2S

(1) Mercurous compounds are decomposed by 1 N sodium hydroxide, producing a black color.

Hg2(NO3)2 + 2 NaOH Hg2(OH)2 + 2 NaNO3 (Soine & Wilson, 1967, p.425) Hg2(OH)2 Hg2 O + H2O Hg2(NO3)2 + 2 NaOH Hg2O + H2O + 2 NaNO3 Hg2(NO3)2 + 2 HCl 2 Hg2 Cl2 + 2 HNO3 (Svehla, 1996, p.98) (hv) Hg2 Cl2 HgCl2 + Hg (Holtzclaw & Robinson, 1988, p.842) Hg2 Cl2 + 2 NH3 Hg + Hg(NH2)Cl + NH4Cl (Svehla, 1996, p.68)

Black-brown precipitate (Soine & Wilson, 1967, p.425)

(2) With hydrochloric acid, solutions of mercurous salts yield a white precipitate

White, crystalline precipitate (Holtzclaw & Robinson, 1988, p.842) Grayish to black precipitate

Mercurous

that is blackened by 6 N ammonium hydroxide.

Black precipitate distributed among white precipitate, which looks as shiny black (Svehla, 1996, p.68)

(3) With potassium iodide TS, a yellow precipitate, that may become green upon standing, is formed.

Hg2(NO3)2 + 2 KI Hg2 I2 + 2 KNO3 (Soine & Wilson, 1967, p.425)

Yellow precipitate which turns green upon standing (Soine & Wilson, 1967, p.425)

Double displacement reaction. ! When KI is in excess of the Hg2(NO3)2, a black precipitate of metallic Hg is obtained, thus KI solution is always added to the Hg2(NO3)2 with constant agitation (Parks et al, 1949, p.57). When boiling it with H2O, disproportionation takes place, and a mixture of HgI & finely distributed black is formed (Svehla, 1996, p.70).

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(1) With hydrochloric acid, solutions of silver salts yield a white, curdy precipitate that is

AgNO3 + HCl AgCl + HNO3 (Svehla, 1996, p.72) (hv) 2 AgCl 2 Ag + Cl2 (Svehla, 1996, p.73) AgCl + HNO3 no reaction (Svehla, 1996, p.72) AgCl + NH4OH [Ag(NH3)2]Cl + H2O (Svehla, 1996, p.191) AgNO3 + NaOH AgOH + NaNO3 ; 2 AgOH Ag2O + H2 O -----------------------------------------------------------2 AgNO3 + 2 NaOH Ag2O + H2 O + 2 NaNO3 (Soine & Wilson, 1967, p.329) Ag2 O + 4 NH4OH 2 Ag(NH3)2OH + 3 H2O (Soine & Wilson, 1967, p.329) HCHO + 2 Ag(NH3)2OH HCOONH4 + 2 Ag + 3 NH3 + H2O (Soine & Wilson, 1967, p.329)

White, curdy precipitate (Svehla, 1996, p.72) Grayish or black precipitate (Svehla, 1996, p.73) No dissolution of precipitate; white, curdy precipitate persists (Svehla, 1996, p.72) Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.191)

Double displacement precipitation reaction. AgCl is soluble in dilute NH4OH, AgBr dissolves in 0.880 ammonia, and AgI is insoluble even in 0.880 ammonia (Lee, 1996, p.825). Sunlight or uv irradiation decomposes silver halides, which turn to grayish or balck owing to the formation of silver metal. The reaction is slow though (Svehla ,1996, p.73).

a.

insoluble in nitric acid, but is

b. readily soluble in 6N ammonium hydroxide. Silver (I)

Formation of the complex silver ammonia cation. Silver chloride ionizes to a greater extent than does silver ammonia complex cation (in an excess of NH4 OH) and, therefore, silver ions are used up in the formation of complex cation (Soine & Wilson, 1967, p.329). Caution! See Bromide. Double displacement reaction between AgNO3 + NaOH while AgOH goes decomposition. Silver fulminate Ag-C2 N2O2 (Most, 1988, p.519) VS Ag3N from Svehla. Precipitate dissolves though complex ion formation (Holtzclaw & Robinson, 1988, p.943). Redox reaction. Tollens reagent is an oxidizing agent while the reducing agents can be formaldehyde, glucose, hypophosphites, eugenol, hydrazine sulfate from Vogels (Soine & Wilson, 1967, p.329). Principle Involved/ Notes Double displacement precipitation reaction. Antimony (III) acts both as a metal and non-metal while the pentavalent condition is almost exclusively as a nonmetal (Soine & Wilson, 1967, p.545). Sb2S3 is stibnite or antimony glance (Parks et al, 1949, p.149). The solution should be strongly acidified to prevent hydrolysis of SbCl6- giving a white precipitate of antimony oxychlorides (Gilreath, 1945, p.198) or kept as the complex ion [SbCl4]- (Soine & Wilson, 1967, p.545). NH4OH neutralizes HCl.

(2) A solution of silver salt to which 6 N ammonium hydroxide and a small quantity of formaldehyde TS are added deposits, upon warming, a mirror of metallic silver upon the sides of the container. Tollens Test; Silver mirror test

Brown precipitate (Soine & Wilson, 1967, p.329) Dissolution of precipitate forming a solution (Soine & Wilson, 1967, p.329) Silver mirror on the walls of the test tube with ammonia odor (Soine & Wilson, 1967, p.329)

Group 2 Cations (Group II Sulfides)

Description of the Tests (from USP 30 NF 25)

Corresponding Equations

Perceptible Result(s)

(1) With hydrogen sulfide, solution of antimony (III) compounds, strongly acidified with hydrochloric acid, yield an orange precipitate of antimony sulfide that is Antimony (III) a. insoluble in 6 N ammonium hydroxide

2 SbCl3 + 3 H2 S Sb2S3 + 6 HCl (Svehla, 1996, p.100)

Orange-red precipitate (Svehla, 1996, p.100)

Sb2 S3 + NH4 OH no reaction (USPCI, 2006, p.139) Sb2 S3 + (NH4)2S 2 NH4SbS2 (Soine & Wilson, 1967, p.547) Bi + 4 HNO3 Bi(NO3)3 + NO2 + H2O (Soine & Wilson, 1967, p.551) BiOCl + 2 HCl BiCl3 + H2O (Gilreath, 1954, p.187) BiCl3 + 2 H2O Bi(OH)2Cl + 2 HCl upon standing: Bi(OH)2Cl BiOCl + H2O (Soine & Wilson, 1967, p.551)

b. but is soluble in ammonium sulfide TS

No dissolution of precipitate; orange precipitate persists(USPCI, 2006, p.139) Dissolution of precipitate forming a solution (Soine & Wilson, 1967, p.547) Reddish brown fumes (Lee, 1996, p.501) Dissolution of white solids to form a clear, colorless solution H2O (Gilreath, 1954, p.187) White precipitate (Soine & Wilson, 1967, p.551)

(1) When dissolved in a slight excess of nitric acid or hydrochloric acid, Bismuth (III) bismuth salts yield a white precipitate upon dilution with water.

It forms compounds with oxidation state of +5 only when treated with strong oxidizing agents (Holtzclaw & Robinson, 1988, p.833). The reaction is reversible and the presence of the oxychloride precipitate is dependent upon a low concentration of hydronium ions (Gilreath, 1954, p.187). Hydrolysis allowed precipitation of the oxychloride (Gilreath, 1954, p.187). Basic bismuth chloride loses water and is converted into the

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oxychloride (Soine & Wilson, 1967, p.551). Bi(NO3)3 + H2O Bi(OH)2NO3 + 2 HNO3 (Soine & Wilson, 1967, p.551) 2 BiCl3 + 3 H2S + 6 H2 O Bi2S3 + 6 HCl (Soine & Wilson, 1967, p.551) Bi2 S3 + 4 HNO3 2 Bi(NO3)3 + NO + 2 H2O + 3 S (Soine & Wilson, 1967, p.551) 2 NO + O2 2 NO2 (Soine & Wilson, 1967, p.62) CuSO4 + Fe FeSO4 + Cu (Soine & Wilson, 1967, p.320) White precipitate (Soine & Wilson, 1967, p.551) Brownish-black precipitate Soine & Wilson, 1967, p.551) Dissolution of precipitate forming a solution and leaving a white precipitate (Svehla, 1996, p. 80), bubbling and reddish brown fumes (Lee, 1996, p.501) Red film deposited on the iron nail (Soine & Wilson, 1967, p.320) The same goes with the oxynitrate. Double displacement precipitation reaction Bismuth nitrate is not soluble in water unless an excess of nitric acid is present because of the formation of insoluble basic bismuth nitratesby the hydrolytic action of water (Parks et al, 1949, p.183). Oxidation of NO to NO2. Single replacement reaction. The position of copper in the electromotive series is responsible for its ability to plate out on metallic iron. Since iron is higher in the series than is copper, the copper is displaces from solution by the iron, which becomes ionized (Soine & Wilson, 1967, p.320). If the solution contains ammonium salts (or it was highly acidic and larger amounts of ammonia were used up for its neutralization), precipitation does not occur at all, but the blue color is formed right away. The reaction is characteristic for copper (II) ions in the absence of nickel (Svehla, 1996, p.84). When OH- ions are added to cold solutions of Cu(II) salts, Cu(OH) 2 is formed while with hot solutions CuO is obtained (Holtzclaw & Robinson, 1988, p.819). Complexation. The blue precipitate dissolves because the complex removes Cu2+ from the solution, thus disturbing the equilibrium between the slightly ionized Cu(OH)2 and its constituent ions, and the Cu(OH)2 keeps dissolving in an effort to supply the demand for Cu2+ (Soine & Wilson, 1967, p.319). The hydrated ion [Cu(H2 O)6]2 is formed when the hydroxide or carbonate are dissolved in acid, or when CuSO4 or Cu(NO3)2 are dissolved in water (Lee, 1996, p.827). Copper possesses the property of forming both complex cations and anions that are quite stable (Holzclaw & Robinson, 1988, p.821). The blue color of aqueous solutions of Cu2+ salts may be due to Cu2+ but some exhibit green or brown, which may be due to the undissociated molecules (Soine & Wilson, 1967, p.318). Double displacement reaction.

This precipitate is colored brown by hydrogen sulfide, and the resulting compound dissolves in a warm mixture of equal parts of nitric acid and water. (1) Solutions of cupric compounds, acidified with hydrochloric acid, deposit a red film of metallic copper upon a bright, untarnished surface of a metallic iron.

(2) An excess of 6 N ammonium hydroxide, added to a solution of cupric salt, produces a bluish precipitate

2 CuSO4 + 2 NH3 + 2 H2O Cu(OH)2 CuSO4 + (NH4)2SO4 (Svehla, 1996, p.84)

Blue precipitate (Svehla, 1996, p.84)

Copper (II) Cu(OH)2 CuSO4 + 8 NH3 [Cu(NH3)4](OH)2 + [Cu(NH3)4]SO4 (Svehla, 1996, p.84) Dissolution of blue precipitate forming a deep-blue solution (Svehla, 1996, p.84)

and then a deep blue-colored solution.

(3) With potassium ferrocyanide TS, solutions of cupric salts yield a reddishbrown precipitate, a. insoluble in diluted acids. Lead (II) Mercury

2 CuSO4 + K4Fe(CN)6 Cu2Fe(CN)6 + 2 K2SO4 (Soine & Wilson, 1967, p.320) Cu2 Fe(CN)6 + HCl no reaction (Soine & Wilson, 1967, p.320)

Reddish-brown precipitate (Soine & Wilson, 1967, p.320) No dissolution of precipitate; reddish-brown precipitate persists (Soine & Wilson, 1967, p.320)

Mercuric

See pp.1-2. See pp.2-3 for the reactions of mercuric ion with the general test for mercury. HgCl2 + 2 NaOH Hg(OH)2 + 2 NaCl (1) Solutions of mercuric salts yield a yellow Hg(OH)2 HgO + H2O (Soine & Wilson, precipitate with 1 N sodium hydroxide. 1967, p.427) (2) they yield also, in neutral solutions with HgCl2 + 2 KI HgI2 + 2 KCl (Svehla, 1996, potassium iodide TS, a scarlet precipitate p.78) that is a. very soluble in an excess of the reagent. HgI2 + 2 KI K2[HgI4] (Svehla, 1996, p.78)

Brownish-red precipitate which turns yellow (Svehla, 1996, p.78) Yellow precipitate which quickly turns red (Soine & Wilson, 1967, p.426) Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.78)

The hydroxide that is first formed, spontaneously decomposes into the oxide and water (Soine & Wilson, 1967, p.426) Double displacement reaction. Alkalined potassium tetraiodomercurate(II) serves as a selective and sensitive reagent for ammonium ions (Nesslers reagent) (Svehla, 1996, p.78); Valsers reagent (Soine & Wilson, 1967, p.426)

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Group 3 Cations (Group III Sulfides and Hydroxides)

Description of the Tests (from USP 30 NF 25) (1) With 6 N ammonium hydroxide, solutions of aluminum salts yield a gelatinous, white precipitate, that is a. insoluble in an excess of 6 N ammonium hydroxide (2) 1 N sodium hydroxide or

Corresponding Equations AlCl3 +3 NH3 + 3 H2O Al(OH)3 + 3 NH4Cl (Svehla, 1996, p.119) Al(OH)3 + NH4OH no reaction (Svehla, 1996, p.119) AlCl3 + 3 NaOH Al(OH)3 + 3 NaCl (Svehla, 1996, p.119) Na2 S + H2O NaSH + NaOH ; NaSH + H2O H2S + NaOH (Svehla, 1996, p. 174) 2 AlCl3 + 3 Na2 S + 6 H2O 2 Al(OH)3 + 3 H2S + 6 NaCl (Svehla, 1996, p. 120; Soine & Wilson, 1967, p. 451) Al(OH)3 + NaOH NaAlO2 + 2 H2O (Soine & Wilson, 1967, p. 451) OR Al(OH)3 + NaOH Na[Al(OH)4] (Svehla, 1996, p. 119) Al(OH)3 + Na2S + 2 H2O Na [Al(OH)4] + H2S + 6 NaCl (Svehla, 1996, p. 118)

Perceptible Result(s)

Principle Involved/ Notes

Gelatinous, white precipitate No dissolution of precipitate; gelatinous, white precipitate persists (Svehla, 1996, p.119) Gelatinous, white precipitate (Svehla, 1996, p.119) Gelatinous, white precipitate (Svehla, 1996, p. 120) with rotten egg odor (Holtzclaw & Robinson, 1988, p.667) Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p. 119) Dissolution of precipitate forming a clear, colorless solution with rotten egg odor (Holtzclaw & Robinson, 1988, p.667)

Double displacement precipitation reaction. The solubility is decreased in the presence of ammonium salts (Svehla, 1996, p.119). Double displacement precipitation reaction. The acid, normal and polysulfides of alkali metals are soluble in water; their aqueous solutions exhbit an alkaline reaction because of hydrolysis (Svehla, 1996, p. 174). NaOH is a strong base and thus can give the necessary OH- for the soluble [Al (OH)4]- to be formed. Al(OH)3 shows acidic properties, forming sodium aluminate. With very weak acidic properties, it is precipitated by CO2 (Lee, p.382) The hydrolysis of S2- is strong enough to provide the necessary OH- for the complex to be formed (Svehla, 1996, p.174).

Aluminum(III)

sodium sulfide TS produces the same precipitate, which

a. dissolves in an excess of either of these reagents (1 N sodium hydroxide)

b. sodium sulfide TS

(1) Solutions of cobalt salts (1 in 20) in 3 N hydrochloric acid yield a red precipitate when heated on a steam bath with an equal volume of a hot, freshly prepared solution of 1-nitroso-2-naphthol (1 in 10) in 9N acetic acid. Cobalt (II) (2) Solutions of cobalt salts, when saturated with potassium chloride and treated with potassium nitrite and acetic acid, yield a yellow precipitate. b. in 6 N ammonium hydroxide.

Reddish-brown precipitate (Svehla, 1996, p.130) CoCl2 + Co(C10H6O2N)3 (Svehla, 1996, p.130) CoCl2 + 6 KNO2 + HNO2 + CH3COOH Co(NO2)3 3 KNO2 + 2KCl + CHOOK + H2O + NO (Soine & Wilson, 1967, p.633) 2 NO + O2 2 NO2 (Soine & Wilson, 1967, p.62) AgI + NH4OH no reaction (Svehla, 1996, p.196) Fe (II): FeCl2 + (NH4)2S FeS + 2NH4Cl (Svehla, 1996, p.110)

Formation of a chelate complex (Svehla, 1996, p.130)

Yellow precipitate (Soine & Wilson, 1967, p.633) and reddish brown fumes (Lee, 1996, p.501) No dissolution of precipitte, which persists (Svehla, 1996, p.196) Double displacement precipitation reaction between FeCl2 + (NH4)2S. Followed by redox, and lastly the oxidation of FeS to basic iron(III) sulfate (Svehla, 1996, p.110). Sulfide ppt: The reaction is exothermal. So much heat can be produced and may catch fire, thus never placed in a waste bin but washed way under running water; only the filter paper should be thrown away (Svehla, 1996, p.114). Fe3+ is not reduced by sulfide. Reaction is obtained in alkaline solutions (Svehla, 1996, p.114).

Iron

General test: Ferrous and ferric compounds in solution yield a black precipitate with ammonium sulfide TS.

4 FeS + 6 H2 O + 3 O2 4 Fe(OH)3 + 4 S (Svehla, 1996, p.114) OR 4 FeS + 9 O2 2 Fe2 O(SO4)2 (Svehla, 1996, p.110) Fe (III): (a) 2 FeCl3 + 3 (NH4)2S Fe2 S3+ 6 NH4 Cl (Soine & Wilson, 1967, p.606) OR

Black precipitate, which becomes brown upon exposure to air (Svehla, 1996, p.110)

Black precipitate (Svehla, 1996, p.114)

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a. This precipitate is dissolved by cold 3 N hydrochloric acid with the evolution of hydrogen sulfide.

(b) 2 FeCl3 + 3 (NH4)2S 2 FeS + S + 6 NH4 Cl (Svehla, 1996, p.114) 4 FeS + 6 H2 O + 3 O2 4 Fe(OH)3 + 4 S (Svehla, 1996, p.114) From Fe (II): FeS + 2HCl FeCl2 + H2 S (Svehla, 1996, p.110) [4 FeS + 6 H2O + 3 O2 4 Fe(OH)3 + 4 S (Svehla, 1996, p.114) ] From Fe (III) (a): Fe2 S3+ 4 HCl 2 FeCl2 + 2 H2S + S (Svehla, 1996, p.114) From Fe (III) (b): FeS + 2HCl FeCl2 + H2 S (Svehla, 1996, p.110)

Redox reaction. This reaction occurs in acidic conditions (Svehla, 1996, p.114). Dissolution of precipitate forming a clear, colorless solution with rotten egg odor (Holtzclaw and Robinson, 1988, p.667) Dissolution of black precipitate forming a green solution while white precipitate becomes visible (Svehla, 1996, p.114) with rotten egg odor (Holtzclaw and Robinson, 1988, p.667) Intense blue precipitate (Svehla, 1996, p.115) (Prussian blue)

Double displacement reaction.

Double displacement reaction / redox.

Double displacement reaction. Double displacement reaction. Sensitive test for ferric ion (Soine & Wilson, 1967, p.605). If FeCl3 is added to an excess of potassium hexacyanoferrate(II), a product with the composition of KFe[Fe(CN)6] is formed and this tends to form the colloidal solutions (Soluble Prussian bue) and cannot be filtered (Svehla, 1996, p.115) Double displacement reaction. Fe(OH)3 is insoluble in excess of the reagent (distinction from aluminum and chromium) (Svehla, 1996, p.113). Fluorides and mercury (II) ions bleach the color (more stable hexafluoroferrate (II) [FeF 6]3-; non-dissociated Hg(SCN)2). The presence of nitrites should be avoided since they also produce red color (nitrosyl thiocyanate, NOSCN), which disappears on heating (Svehla, 1996, p.116). Vogel reaction, especially for Co2+ (Svehla, p.129).

(1) Acid solutions of ferric salts yield a dark blue precipitate with potassium ferrocyanide TS (yellow prussiate of potash)

4 FeCl3 + 3 K4[Fe(CN)6] Fe4[Fe(CN)6]3 + 12 KCl (Svehla, 1996, p.115)

(2) With an excess of 1 N sodium hydroxide, a reddish-brown precipitate. Ferric

FeCl3 + 3 NaOH Fe(OH)3 + 3 NaCl (Svehla, 1996, p.113)

Reddish-brown precipitate; brown gelatinous precipitate (Soine & Wilson, 1967, p.605)

(3) With ammonium thiocyanate TS, solutions of ferric salts produce a deep red color

3 FeCl3 + 3 NH4SCN + 5 H2O 3 [Fe(H2O)5SCN]Cl2 + 3 NH4Cl (Holtzclaw and Robinson, 1988, p.812)

Deep-red solution (USP CI, 2006, p.140)

that is not destroyed by dilute mineral acids

Fe(SCN)3 + HCl non-dissociated Fe(SCN)3 (Svehla, 1996, p.116)

Blood-red solution (Holtzclaw and Robinson, 1988, p.812) Dark blue precipitate (Soine & Wilson, 1967, p.605) (Turbulls blue) Double displacement reaction. Sensitive test for ferrous ion. !! The identical composition and structure of Prussian blue and Turnbulls blue has recently been proved by Mssbauer spectroscopy. Turnbulls blue formation: Fe2+ + [Fe(CN)6]3- Fe3+ + [Fe(CN)6]4- First hexacyanoferrrate (III) ions oxidize ferrous to ferric, when hexacyanoferrate(II( is formed and these ions combine to a precipitate called Turnbulls blue: 4 Fe3+ + 3 [Fe(CN)6]4- Fe4[Fe(CN)6]3 <same composition with Prussian blue!> (Svehla, 1996, p.111).

(1) Solutions of ferrous salts yield a dark blue precipitate with potassium ferricyanide TS (red prussiate of potash)

3 FeSO4 + 2 K3[Fe(CN)6] Fe3 [Fe(CN)6]2 + 3 K2 SO4 (Soine & Wilson, 1967, p.605)

Ferrous a. This precipitate is insoluble in 3 N hydrochloric acid but Fe3 [Fe(CN)6]2 + HCl no reaction (Soine & Wilson, 1967, p.606) No dissolution of precipitate; dark blue precipitate persists (Soine & Wilson, 1967, p.606)

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b. is decomposed by 1 N sodium hydroxide.

Fe3 [Fe(CN)6]2 + 8 NaOH 2 Na4[Fe(CN)6] + 2 Fe(OH)3 + Fe(OH)2 (Soine & Wilson, 1967, p.606) 4 Fe(OH)2 + 2H2 O + O2 4 Fe(OH)3 (Svehla, 1996, p.110)

Dark blue precipitate turned gelatinous, brown and green; the green precipitate turned brown on shaking forming a dirty-green appearance (Svehla, 1996, p.110) Greenish-white precipitate, which rapidly changes to green (Soine & Wilson, 1967, p.606) and then to brown, forming a dirty-green appearance (Svehla, 1996, p.110) Pink precipitate (Svehla, 1996, p.137) Dissolution of precipitate forming a solution (Svehla, 1996, p.137) with rotten egg odor (Holtzclaw & Robinson, 1988, p.667)

Decomposition of Fe3 [Fe(CN)6]2 (Soine & Wilson, 1967, p.606)

Redox.

(2) With 1 N sodium hydroxide, solutions of ferrous salts yield a greenish-white precipitate, the color changing rapidly to green and then to brown when shaken. (1) With ammonium sulfide TS, solutions of manganese salts yield a salmon-colored precipitate that a. dissolves in acetic acid.

FeSO4 + 2 NaOH Fe(OH)2 + Na2 SO4 (Svehla, 1996, p.110) 4 Fe(OH)2 + 2H2 O + O2 4 Fe(OH)3 (Svehla, 1996, p.110) MnCl2 + (NH4)2S MnS + 2 NH4Cl (Svehla, 1996, p.137) MnS + 2 CH3 COOH Mn(CH3COO)2 + H2S (Svehla, 1996, p.137) ZnSO4 + H2 S ZnS + H2SO4 (Svehla, 1996, p.140) ZnSO4 + 2 H2S + 2 CH3COONa ZnS + H2 SO4 + 2 CH3COOH + Na2 SO4 ZnS + CH3COOH no reaction (Soine & Wilson, 1967, p.408) ZnS + 2 HCl ZnCl2 + H2S (Gilreath, 1954, p.210). ZnSO4 + (NH4)2S ZnS + (NH4)2SO4 (Soine & Wilson, 1967, p.407) 2 ZnSO4 + K4[Fe(CN)6] Zn2[Fe(CN)6] + 2 K2SO4 (Soine & Wilson, 1967, p.408) Zn2[Fe(CN)6] + HCl no reaction (Soine & Wilson, 1967, p.408)

Double displacement reaction.

Redox. Double displacement reaction.

Manganese (II)

Double displacement reaction. Distinction from nickel, cobalt and zinc. ZnS is the only white sulfide precipitate. Sodium acetate is added to the solution because it reduces H + as it forms the feebly dissociated acetic acid, thus the sulfide-ion concentration is correspondingly increased, and precipitation is almost complete (Svehla, 1996, p.140). Acetic acid is a weak acid and not to provide enough H3O+ to solubilize the sulfide: ZnS + 2 H3 O+ Zn2+ + H2S + 2 H2 O (Gilreath, 1954, p.210). Acetic acid is a weak acid and not to provide enough H3O+ to solubilize the sulfide: ZnS + 2 H3 O+ Zn2+ + H2S + 2 H2 O (Gilreath, 1954, p.210).

(1) In the presence of sodium acetate, solutions of zinc salts yield a white precipitate with hydrogen sulfide.

White precipitate (Svehla, 1996, p.140)

a. This precipitate is insoluble in acetic acid,

Zinc (II)

b. but is dissolved by 3 N hydrochloric acid. (2) Ammonium sulfide TS produces a similar precipitate in neutral and alkaline solutions. (3) With potassium ferrocyanide TS, zinc salts in solution yield a white precipitate that is a. insoluble in 3 N hydrochloric acid.

No dissolution of precipitate; white precipitate persists (Soine & Wilson, 1967, p.408) Dissolution of precipitate forming a clear, colorless solution (Gilreath, 1954, p.210) with rotten egg odor (Holtzclaw & Robinson, 1988, p.667) White precipitate (Soine & Wilson, 1967, p.407) White precipitate (Soine & Wilson, 1967, p.408) No dissolution of precipitate; white precipitate persists(Soine & Wilson, 1967, p.408) Perceptible Result(s)

Double displacement reaction.

Double displacement reaction.

Group 4 Cations (Group IV Carbonates) Barium (II)

Description of the Tests (from USP 30 NF 25) (1) Solutions of barium salts yield a white precipitate with 2 N sulfuric acid a. this precipitate is insoluble in hydrochloric acid and nitric acid

Corresponding Equations BaCl2 + H2 SO4 BaSO4 + 2 HCl (Svehla, 1996, p. 145) BaSO4 + HCl no reaction BaSO4 + HNO3 no reaction (Svehla, 1996, p. 145)

Principle Involved/ Notes Double displacement precipitation reaction. The solubility of very small crystals is greater than that of larger ones with pronounced effect in hard crystals, like BaSO4, due to surface

Heavy, white precipitate (Svehla, 1996, p. 145) No dissolution of precipitate; white precipitate persists (Svehla, 1996, p. 145)

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(2) Barium salts impart a yellowish-green color to a nonluminous flame that appears blue when viewed throughgreen glass. Solutions of calcium salts form insoluble oxalates when treated as follows. (1) To a solution of the calcium salt (1 in 20) add 2 drops of methyl red TS, and neutralize with 6 N ammonium hydroxide. Add 3 N hydrochloric acid, dropwise, until the solution is acid to the indicator. Upon the addition of ammonium oxalate TS a white precipitate is formed. Calcium (II) a. This precipitate is insoluble in 6 N acetic acid b. but dissolves in hydrochloric acid. (2) Calcium salts moistened with hydrochloric acid impart a transient yellowish-red color to a nonluminous flame. Group 5 Cations Soluble Ions) Description of the Tests (from USP 30 NF 25) (1) Ammonium salts are decomposed by the addition of an excess of 1 N sodium hydroxide, with the evolution of ammonia, recognizable by its odor and by its alkaline effect upon moistened red litmus paper exposed to the vapor. Warming the solution accelerates the decomposition.

BaCl2 Ba + 2 Cl, Ba Ba*, Ba* Ba + hv (Petrucci and Harwood, 1997, p.766)

Yellowish-green flame (Svehla, 1996, p.7) or weak and fleeting yellowishgreen flame (Holtzclaw & Robinson, p.986)

energy (Gilreath, 1954, p.96). The energy from the flame excites an electron to a higher energy level, and when it falls back to the lower energy level the extra energy is given out as light (Lee, 1996, p.287). Double displacement reaction. Calcium oxalate tends to form supersaturated solutions and may not precipitate unless the solution is heaed (Gilreath, 1954, p.217).

CaCl2 + (NH4)2 (COO)2 Ca(COO)2 + 2 NH4Cl (Svehla, 1996, p.150)

White, crystalline precipitate (Svehla, 1996, p.234)

Ca(COO)2 + CH3COOH no reaction (Svehla, 1996, p.150) Ca(COO)2 + 2 HCl CaCl2 + H2 O + CO + CO2 (Svehla, 1996, p.234) CaCl2 Ca + 2 Cl, Ca Ca*, Ca* Ca + hv (Petrucci and Harwood, 1997, p.766)

No dissolution of precipitate; precipitate persists (Svehla, 1996, p.150) Dissolution of precipitate forming a clear, colorless solution, which bubbles (Svehla, 1996, p.234) Transient yellowish-red flame (Soine & Wilson, 1967, p.375) or brick-red (yellowish) flame (Svehla, 1996, p.7) Perceptible Result(s)

Decomposition of oxalate (Svehla, 1996, p.234) The energy from the flame excites an electron to a higher energy level, and when it falls back to the lower energy level the extra energy is given out as light (Lee, 1996, p.287). Principle Involved/ Notes

Corresponding Equations NH4Cl + NaOH NH3 + H2O + NaCl (Soine & Wilson, 1967, p.238) NH3 + H2O NH4+ + OH- (Hotzclaw, 1988, p.994) NH4OH NH4+ + OHNH4Cl NH4+ + Cl- (Soine & Wilson, 1967, p.355)

Ammonium(I)

Ammonia odor (Soine & Wilson, 1967, p.302)

red litmus turns blue (Hotzclaw, 1988, p.994)

Neutralization reaction: NH4+ is essentially an acid which is capable of ionizing into ammonia and a proton, and OH- is a strong base capable of combining with proton. NH4+ NH3 + H+ (Soine & Wilson, 1967, p.302) The chemical reactions of interest that involve Mg2+ are based upon solubility since the divalent ion is neither reduced nor oxidized. NH4OH incompletely precipitates Mg(OH)2 from solution of Mg salts. In the presence of an NH4+ salt, NH4OH does not precipitate Mg2+, because the concentration of OH- produced by the NH4 OH is depressed by the excess of NH4+ from the NH4Cl by the law of mass action. When the concentration of Mg2+is multiplied by the square of the concentration of the OH-, there is obtained a product that is less than the ion-product constant (solubility product) of Mg(OH)2 and hence no precipitate will be formed (Soine & Wilson, 1967, p.355).

(1) Solutions of magnesium salts in the presence of ammonium chloride yield no more than a slightly hazy precipitate when neutralized with ammonium carbonate TS, Magnesium (II)

Slightly hazy precipitate (USP CI, 2006, p.140) MgCl2 + 2 NH4 OH Mg(OH)2 + 2 NH4Cl (Svehla, 1996, p.153)

but on the subsequent addition of dibasic sodium phosphate TS, a white crystalline precipitate, which is

Na2 HPO4 2 Na+ + HPO42HPO42- + NH3 NH4+ + PO43MgCl2 + NH4Cl + Na3 PO4 + 6 H2O MgNH4 PO4 6H2O MgCl2 + Na2 HPO4 + NH3 + 6 H2O MgNH4PO46H2O + 2 NaCl (Soine & Wilson, 1967, p.355) MgNH4 PO4 + NH4 OH no reaction (Soine &

White, crystalline precipitate (Soine & Wilson, 1967, p.355)

NH4Cl prevents precipitation of Mg(OH)2 (Soine & Wilson, 1967, p.356)

insoluble in 6 N ammonium hydroxide, is formed.

White, crystalline precipitate

NH4OH lessens the hydrolysis and decreases the

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Wilson, 1967, p.356)

(Soine & Wilson, 1967, p.355)

(1) Potassium compounds impart a violet color to a nonluminous flame, but the presence of small quantities of sodium masks the color unless the yellow color produced by sodium is screened out by viewing through a blue filter that blocks at 589 nm (sodium) but is transparent to emission at 404 nm (potassium). Traditionally, cobalt glass has been used, but other suitable filters are commercially available. Potassium (I) (2) In neutral, concentrated or moderately concentrated solutions of potassium salts (depending upon the solubility and the potassium content), sodium bitartrate TS produces a white crystalline precipitate that is a. soluble in 6 N ammonium hydroxide and in solutions of alkali hydroxides and carbonates. The formation of the precipitate, which is usually slow, is accelerated by stirring or rubbing the inside of the test tube with a glass rod. The addition of a small amount of glacial acetic acid or alcohol also promotes the precipitation. (1) Unless otherwise specified in an individual monograph, prepare a solution to contain 0.1 g of the sodium compound in 2 mL of water. Add 2 mL of 15% potassium carbonate, and heat to boiling. No precipitate is formed. Add 4 mL of potassium pyroantimonate TS, and heat to boiling. Allow to cool in ice water, if necessary, rub the inside of the test tube with a glass rod. A dense precipitate is formed. (2) Sodium compounds impart an intense yellow color to a nonluminous flame.

KCl K + Cl, K K*, K* K + hv (Petrucci and Harwood, 1997, p.766)

Violet (lilac) (Svehla, 1996, p.7)

solubility of the salt MgNH4PO4 + H2O Mg2+ + HPO42- + NH4OH (Soine & Wilson, 1967, p.356) Color arises because the energy absorbed or emitted in electronic transition corresponds to a wavelength in the visible region. Alkali Metal ions all have noble gas configurations in which all the electrons are paired. Thus the required energy in promoting an electron is large since some for unpairing an electron, some for breaking a shell of electrons and some to promote to a higher energy level. Hence no transition and the compounds are typically white, except those where the anion is colored (Lee, 1996, p.288). Double displacement reaction. Ammonium salts yield a similar precipitate and must be absent.

KCl + NaHC4H4O6 KHC4H4O6 + NaCl (Svehla, 1996, p.156)

White, crystalline precipitate; granular (Soine & Wilson, 1967, p.270)

Dissolution of precipitate forming a clear, colorless solution (USP CI, 2006, p.141)

K2CO3 2 NaCl + 2 KH2 SbO4 Na2 H2Sb2O7 + 2 KCl + H2O (Soine and Wilson, 1967, p.193)

White, crystalline precipitate (Soine and Wilson, 1967, p.193)

Double displacement reaction.

Sodium (I)

NaCl Na + Cl, Na Na*, Na* Na + hv (Petrucci and Harwood, 1997, p.766) Li2SO4 + NaOH 2 LiOH + Na2 SO4 (Soine and Wilson, 1967, p.188) 2 LiOH + Na2CO3 Li2 CO3 + 2 NaOH (Soine and Wilson, 1967, p.188) Li2CO3 + 2 NH4Cl (NH4)2CO3 + 2 LiCl (Svehla, 1996, p.311) LiCl Li + Cl, Li Li*, Li* Li + hv (Petrucci and Harwood, 1997, p.766) LiCl + H2SO4 no reaction

Persistent golden-yellow flame (Svehla, 1996, p.7)

The energy from the flame excites an electron to a higher energy level, and when it falls back to the lower energy level the extra energy is given out as light (Lee, 1996, p.287).

(1) With sodium carbonate TS, moderately concentrated solutions of lithium salts, made alkaline with sodium hydroxide, yield a white precipitate on boiling. a. The precipitate is soluble in ammonium chloride TS. (2) Lithium salts moistened with hydrochloric acid impart an intense crimson color to a nonluminous flame. (3) Solutions of lithium salts are not precipitated by 2 N sulfuric acid or soluble sulfates (distinction from strontium)

White precipitate on boiling (Soine and Wilson, 1967, p.188) Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.311) Intense crimson flame (USP Ci, 2006, p.140) No white precipitate (Svehla, 1996, p.147)

Li2CO3 is not very souble and precipitates from solution more readily than the other alkali metal carbonates (Holtzclaw & Robinson, 1988, p.375). No precipitation occurs in the presence of high concentrations of NH4Cl since the carbonate-ion concentration is reduced to such an extent that the solubility product of Li2CO3 is not exceeded (Svehla, 1996, p.311). The energy from the flame excites an electron to a higher energy level, and when it falls back to the lower energy level the extra energy is given out as light (Lee, 1996, p.287).

Lithium (I)

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Anions may be classified according to the processes employed and the corresponding results or reactions. Class A anions: those involving the identification by volatile products obtained on treatment with acids. It is subdivided into: (1) gases evolved with dilute HCl or H2 SO4, and (2) gases or vapors evolved with concentrated H2SO4, includes also anions in (1) Class B anions: those dependent upon reactions in solution. It is subdivided into: (1) precipitation reactions (2) oxidation and reduction in solution (Svehla, 1996, p.163). Anions may also be separated into groups based upon the solubilities of Calcium, Barium, Cadmium, and Silver salts. 1 Group I includes ions whose calcium salts are insoluble in neutral or slightly basic solution. Anions under this group are AsO 42-, AsO2-, CO32-, F-, C2O4-, PO43-, and SO32-. 2 Group II includes ions whose calcium salts are soluble but whose barium salts are insoluble slightly basic solution. Anions u nder this group are CrO4- and SO42-. 3 Group III is composed of anions whose calcium and barium salts are soluble but whose cadmium salts are insoluble slightly bas ic solution. Anions under this group are [Fe(CN) 6]3-, [Fe(CN)6]4- andS2-.There are no any official identification tests for these Group III anions. 4 Group IV is composed of anions whose calcium, barium and cadmium salts are soluble but whose silver salts are insoluble in a solution slightly acid with nitric acid. Anions under this group are Br --,, Cl-, I-, CNS- and S2 O32-. 5 Group V contains anions whose calcium, barium, cadmium and silver salts are soluble in water and acids. Anions under this group are B4O72-, ClO3-, NO3-, and NO2- (Gilreath, 1954, p.225). *not included in this scheme. ANION Class A (1) DESCRIPTION OF THE TESTS Gases evolved with dilute HCl or H2 SO4 (1) Carbonate and bicarbonates effervesce with acids evolving a colorless gas that, Carbonate1 when passed into calcium hydroxide TS, produces a white precipitate immediately. (2) A cold solution (1 in 20) of a soluble carbonate is colored red by phenolphthalein TS, while a similar solution of BICARBONATE remains unchanged or is slightly only colored. (1) when treated with 3 N hydrochloric acid, sulfites and bisulfites yield sulfur dioxide, which blackens filter paper moistened with mercurous nitrate TS. (1) With hydrochloric acid, solutions of thiosulfates yield a white precipitate that turns yellow, and sulfur dioxide, which blackens filter paper moistened with mercuruous nitrate TS. (2) The addition of ferric chloride TS to solutions of thiosulfates produces a dark violet color that quickly disappears. CORRESPONDING EQUATIONS CaCO3 + 2 HCl CaCl2 + CO2 + H2O (Svehla, 1996, p.164) CO2 + Ca(OH)2 CaCO3 + H2O (Svehla, 1996, p.164) PERCEPTIBLE RESULTS Bubbling of the solution (Svehla, 1996, p.164) The clear, colorless solution becomes turbid (Svehla, 1996, p.164) Red solution (USP CI, 2006, p.140) Slightly pinkish solution (USP CI, 2006, p.140) Suffocating odor of burning sulfur or acrid odor (Svehla, 1996, p.168) Filter paper turns black (Soine and Wilson, 1967, p.575) White precipitate that turns yellow with acrid odor or suffocating odor of burning sulfur (Svehla, 1996, p.171) Filter paper turns black (Soine and Wilson, 1967, p.575) Dark-violet solution (Svehla, 1996, p.173) Upon standing the violet color disappears and a green solution may be formed (Svehla, 1996, p.173) PRINCIPLE INVOLVED/ NOTES Decomposition od the carbonate (Svehla, 1996, p.164) Neutralization reaction.

(Bicarbonate)*

Na2 SO3 + 2 HCl SO2 + H2 O + 2 NaCl (Svehla, 1996, p.168) SO2 + Hg2(NO3)2 + 2 H2 O 2 Hg + 2 HNO3 + H2 SO4 (Soine and Wilson, 1967, p.575) Na2 S2O3 + 2 HCl 2 NaCl + H2S2 O3 ; H2S2O3 S+ SO2 + H2O -----------------------------------------------------------Na2 S2O3 + 2 HCl 2 NaCl + S+ SO2 + H2O (Svehla, 1996, p.171) SO2 + Hg2(NO3)2 + 2 H2 O 2 Hg + 2 HNO3 + H2 SO4 (Soine and Wilson, 1967, p.575) 2 Na2S2O3 + FeCl3 Na[Fe(S2 O3)2] + 3 NaCl (Svehla, 1996, p.173) Na[Fe(S2O3)2] + FeCl3 Fe(S4O6) + FeCl2 + NaCl (Svehla, 1996, p.173)

Decomposition (Svehla, 1996, p.168) Redox with the mercurous nitrate reduced to metallic mercury (Soine and Wilson, 1967, p.575) Disproportionation reaction. Sodium thiosulfate is unstable in the presence of acids because free thiosulfuric acid is liberated (Parks et al, 1949, p.144). Redox with the mercurous nitrate reduced to metallic mercury (Soine and Wilson, 1967, p.575) Double displacement reaction. The overall reaction can be written as the reduction of iron(III) by thiosulfate: 2 S2O32- + 2 Fe3+ S4O62- + 2 Fe2+ (Svehla, 1996, p.173) Disproportionation reaction: NO2- + H2O NO3- + 2 H+ + 2 e2 [NO2- + 2 H++ e- NO + H2 O] 3 NO2- + 2 H+ NO3- + 2 NO + H2O

Sulfite1

Thiosulfate4

Nitrite5

(1) When treated with dilute mineral acids or with 6 N acetic acid, nitrites evolve brownish-red fumes.

NaNO2 + HCl HNO2 + NaCl (2 HNO2 H2O + N2O3) 3 HNO2 HNO3 + 2 NO + H2O

Transient, pale-blue solution

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NO + O2 2 NO2 (Svehla, 1996, p.177) 2 HNO2 + 2 KI + 2 HCl I2 + 2 NO + 2 KCl + 2 H2O (Svehla, 1996, p.177) I2 + starch-iodide starch-iodo complex

with reddish-brown fumes (Svehla, 1996, p.177)

The solution colors starch-iodide paper blue. Sulfide3 Hypochlorite* Cyanide* Cyanate* Class A (2)

Blue paper (USP CI, 2006, p.140)

Redox reaction with NO oxidized to NO2. Combination of NO and O2 to form nitrogen dioxide (Svehla, 1996, p.177) Redox reaction with HNO2 acting as an oxidizing agent. Formation of adsorption complex

No official ID test Gases or acid vapors evolved with concentrated H2 SO4, including anion of Class A (1) (1) With silver nitrate TS, solutions of chlorides yield NaCl + AgNO3 AgCl + NaNO3 (Svehla, 1996, p.191) a white, curdy precipitate that is (hv) 2 AgCl 2 Ag + Cl2 (Svehla, 1996, p.73)

White, curdy precipitate (Svehla, 1996, p.191) Grayish or black precipitate (Svehla, 1996, p.73) No dissolution of precipitate; Grayish or black precipitate persists (Svehla, 1996, p.73)

Double displacement precipitation reaction Sunlight or uv irradiation decomposes silver halides, which turn to grayish or balck owing to the formation of silver metal. The reaction is slow though (Svehal ,1996, p.73).

a. insoluble in nitric acid but

AgCl + HNO3 no reaction (Svehla, 1996, p.191)

b. is soluble in a slight excess of 6 N ammonium hydroxide.

AgCl + NH4OH [Ag(NH3)2]Cl + H2O (Svehla, 1996, p.191)

Dissolution of precipitate forming a clear, colorless solution

Formation of the complex silver ammonia cation. Silver chloride ionizes to a greater extent than does silver ammonia complex cation (in an excess of NH4 OH) and, therefore, silver ions are used up in the formation of complex cation (Soine and Wilson, 1967, p.329). Caution! See Bromide.

Chloride4

(2) When testing amine (including alkaloidal hydrochlorides) that do not respond to the above test, add one drop of diluted nitric acid and 0.5 mL of silver nitrate TS to a solution of the substance being examined containing, unless otherwise directed in the monograph, about 2 mg of chloride ion in 2 mL; a white, curdy precipitate is formed Centrifuge the mixture without delay, and decant the supernatant layer. Wash the precipitate with three 1mL portions of niric acid solution (1 in 100), and discard the washings. Add ammonia TS dropwise to this precipitate. It dissolves readily. (3) When a monograph specifies that an article responds to the test for dry chlorides, mix the solid to be tested with an equal weight of manganese dioxide, moisten with sulfuric acid, and gently heat the mixture: chlorine, which is recognizable by the production of a blue color with moistened starch iodide paper, is evolved. (1) Solutions of bromides, upon addition of chlorine TS, dropwise, liberate bromine, 2 NaCl + MnO2 + 2 H2SO4 MnSO4 + Cl2 + 2 H2O + Na2 SO4 OR 2 NaCl + MnO(OH)2 + 2 H2 SO4 MnSO4 + Cl2 + 3 H2 O + Na2 SO4 (Schela, 1996, p.191) Cl2 + KI KCl + I2 I2 + starch starch-iodo complex 4 NaClO + 4 HCl 4 NaCl + 2 Cl2 +O2 + 2 H2 O (Soine and Wilson, 1967, p.243)

White, curdy precipitate (USP CI, 2006, p.140)

Dissolution of precipitate; white precipitrate persists (USP CI, 2006, p.140)

Formation of yellow-green gas with suffocating odor (Schela, 1996, p.191)

Redox reaction.

Paper turned blue (USP CI, 2006, p.140) Greenish yellow gas having characterisitc, unpleasant and

Redox Formation of adsorption complex Redox. In practice, it is more convenient to use

Bromide4

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suffocating odor (Soine and Wilson, 1967, p.82)

2 NaBr + Cl2 Br2 + NaCl (Svehla, 1996, p. 194)

Orange-red solution

dilute sodium hypochlorite solution, acidified with dilute hydrochloric acid to generate chlorine (Svehla, 1996, p.193) Redox. A halogen of lower atomic weight will always displace one of higher atomic weight from its binary hydrogen compounds of from the salts thereof. Cl2 is an oxidizing agent, thus it is reduced as chloride. (Soine and Wilson, 1967, p.76 Solvent extraction Double displacement precipitation reaction. Sunlight or uv irradiation decomposes silver halides, which turn to grayish or black owing to the formation of silver metal. The reaction is slow though (Svehla ,1996, p.73).

which is dissolved by shaking with chloroform, coloring the chloroform red to reddish brown.

Br2 + CHCl3 (Br2)CHCl3 (Shriner et al, 1998, p. 88) SrBr2 + 2 AgNO3 2 AgBr + Sr(NO3)2 (Svehla, 1996, p.193)

Reddish brown solution below the colorless aqueous layer (Svehla, 1996, p. 193) Curdy, pale-yellow precipitate (Svehla, 1996, p.193) Grayish or black precipitate (Svehla, 1996, p.73) No dissolution of precipitate; precipitate persists (Svehla, 1996, p.193)

(2) Silver nitrate TS produces in solutions of bromides a yellowish-white precipitate that is

(hv) 2 AgBr 2 Ag + Br2 (Svehla, 1996, p.73)

a. insoluble in nitric acid and Bromide4 (continued) b. is slightly soluble in 6 N ammonium hydroxide.

AgBr + HNO3 no reaction (Svehla, 1996, p.193)

AgBr + 2 NH4OH [Ag(NH3)2] Br + 2 H2 O (Svehla, 1996, p.191)

Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.191)

Formation of soluble complex. ! The solution obtained dissolving in ammonia should be discarded quickly to avoid explosion or acidified quickly with 2 M nitric acid and disposed of. Otherwise, when set aside, a precipitate of silver nitride Ag3N (fulminating silver) is formed slowly, which explodes readily even in a wet form (Svehla, 1996, p.72). Redox Solvent extraction Formation of adsorption complex Double displacement precipitation reaction Sunlight or uv irradiation decomposes silver halides, which turn to grayish or balck owing to the formation of silver metal. The reaction is slow though (Svehal ,1996, p.73). Ag+ ion is small and highly polarizing and the anion, I-, is large and highly polarizable. This leads to some covalent character (Lee, 1996, p.825).

(1) Solutions of iodides, upon the addition of chlorine TS, dropwise, liberate iodine, which colors the solution yellow to red. When the solution is shaken with chloroform, the latter is colored violet. The iodine thus liberated gives a blue color with starch TS. (2) Silver nitrate TS produces, in solutions of iodides, a yellow, curdy precipitate that is Iodide4

2 NaI+ Cl2 I2 + 2 NaCl (Soine and Wilson, 1967, p.128) I2 + CHCl3 (I2)CHCl3 (Shriner et al, 1998, p. 88) I2 + starch starch-iodo complex (Soine and Wilson, 1967, p.96) NaI + AgNO3 AgI + NaNO3 (Svehla, 1996, p.196) (hv) 2 AgI 2 Ag + I2 (Svehla, 1996, p.73)

Yellow to red solution (USP CI, 2006, p.140) Violet solution below the colorless aqueous layer (Svehla, 1996, p. 196) Blue solution (Soine and Wilson, 1967, p.96) Yellow, curdy precipitate (Svehla, 1996, p.196) Grayish or black precipitate (Svehla, 1996, p.73)

a. insoluble in nitric acid and

AgI + HNO3 no reaction (Svehla, 1996, p.196)

No dissolution of precipitate; Yellow, curdy to grayish or black precipitate persists (Svehla, 1996, p.196) No dissolution of precipitate; Yellow, curdy to grayish or black precipitate persists (Svehla, 1996, p.196)

b. in 6 N ammonium hydroxide.

AgI + NH4OH no reaction (Svehla, 1996, p.196)

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Nitrate5

(1) When a solution of nitrate is mixed with an equal volume of sulfuric acid, the mixture is cooled, and a solution of ferrous sulfate is superimposed, a brown color is produced at the junction of the two liquids. Brown ring test (2) When a nitrate is heated with sulfuric acid and metallic copper, brownish-red fumes are evolved. (3) Nitrates do not decolorize acidified potassium permanganate TS (distinction from nitrites).

6 FeSO4 + HNO3 + 3 H2SO4 2 NO + 3 Fe2(SO4)3 + 4 H2O FeSO4 + NO FeSO4 NO (Soine and Wilson, 1967, p.151) FeSO4 + NO [Fe(NO)]SO4 (Svehla, 1996, p.200) 2 NaNO3 + 4 H2SO4 + 3 Cu Na2 SO4 + 3 CuSO4 + 2 NO + 4 H2O (Svehla, 1996, p.200) 2 NO + O2 2 NO2 (nitric oxide nitrogen dioxide) HNO3 + KMnO4 + H2SO4 no reaction 5 HNO2 + 2 KMnO4 + 3 H2 SO4 5 HNO3 + 2 MnSO4 + 3 H2O + K2SO4 (Soine and Wilson, 1967, p.250)

Formation of purple ring changing to brown at the junction of two liquids (USP CI, 2006, p.140) Blue solution with reddish-brown fumes (Svehla, 1996, p.199) Solution remains purple (USP CI, 2006, p.140) Purple solution becomes colorless with no fumes (Svehla, 1996, p.197) Solution remains clear and colorless but white precipitate may form on standing (Svehla, 1996, p.209) Intense blue color green-bordered flame (Soine and Wilson, 1967, p.210) Characteristic pleasant, fruity odor of ethyl acetate (Svehla, 1996, p.230) Deep-red solution (Svehla, 1996, p.231) White, crystalline precipitate (Svehla, 1996, p.234) No dissolution of precipitate; white, crystalline precipitate persists(Svehla, 1996, p.234) Dissolution of precipitate forming a clear, colorless solution (USP CI, 2006, p.140) Purple solution becomes colorless with bubbling (Svehla, 1996, p.235) No precipitate (Svehla, 1996, p.203) White precipitate (Gilreath, 1954, p.243) No dissolution of precipitate; white precipitate persists (USP CI, 2006,

Redox. Reduction of nitrate to nitric oxide. On shaking and warming the mixture the brown color disappears, nitrogen dioxide is evolved, and a yellow solution of iron(III) ions remains (Svehla, 1996, p.200). Redox. NO3 cannot be further oxidized. It only acts as an oxidizing agent wherein it could be reduced to NO or NO2, NH3 or N2. Redox: NO2- acts as RA.

Nitrate (continued) (1) To 1 mL of a borate solution, acidified with hydrochloric acid to litmus,

Na2 B4O7 + 2 HCl + 5 H2O 4 H3BO3 + 2 NaCl (Svehla, 1996, p.209) 2 I- I2 I2 + (C2 H4O)n adsoprtion complex Na2 B4O7 + H2SO4 + 5 H2O 4 H3 BO3 + 2 Na2 SO4 H3BO3 + 3 CH3 OH (CH3)3BO3 + 3 H2O (Soine and Wilson, 1967, p.210) Zn (CH3COO)2 + 2 H2SO4 + 2 CH3 CH2OH CH3COOCH2CH3 + Zn (HSO4)2 + 2 H2 O (Svehla, 1996, p.230) 3 Zn (CH3COO)2 + 3 FeCl3 + 2 H2 O [Fe3(OH)2(CH3 COO)6]Cl + 3 ZnCl2 + 2 HCl (Svehla, 1996, p.231) (COONa)2 + CaCl2 (COO)2Ca + 2 NaCl (Svehla, 1996, p.234) (COO)2 Ca + CH3COOH no reaction (Svehla, 1996, p.234) (COO)2 Ca + HCl CaCl2 + H2(COO)2 (Gilreath, 1954, p.230) (COONa)2 + 2 KMnO4 + 3 H2SO4 2 CO2 + 2 MnSO4 + 3 H2O + K2 SO4 + Na2 SO4 (Svehla, 1996, p.235) KClO3 + AgNO3 no reaction (Svehla, 1996, p.203) 2 KClO3 + H2SO4 2 HCl + K2SO4 + 3 O2 HCl + AgNO3 AgCl +HNO3 (Gilreath, 1954, p.243) AgCl +HNO3 no reaction (USP CI, 2006, p.140)

Double displacement reaction Due to the borate present in the solution, iodide was oxidized to iodine which forms the blue complex with the alcohol. Esterification of the boric acid to form trimethyborate (Soine and Wilson, 1967, p.210)

Borate5

add 3 or 4 drops of iodine TS and 3 or 4 drops of polyvinyl alcohol solution (1 in 50): an intense blue color is produced. (2) When a borate is treated with sulfuric acid, methanol is added, and the mixture is ignited, it burns with a green-bordered flame. (1) When acetic acid or an acetate is warmed with sulfuric acid and alcohol, ethyl acetate, recognizable by its characteristic odor is evolved (2) With neutral solutions of acetates, ferric chloride TS produces a deep red color that is destroyed by the addition of mineral acids (1) Neutral and alkaline solutions of oxalates yield a white precipitate with calcium chloride TS. a. This precipitate is insoluble in 6 N acetic acid but is b. dissolved by hydrochloric acid. (2) Hot acidified solutions of oxalates decolorize potassium permanganate. (1) Solutions of chlorates yield no precipitate with silver nitrate TS.

Esterification

Acetate*

Complexation Double displacement precipitation reaction. Acetic acid is too weakly acidic to provide enough H3O+ to form the soluble oxalic acid (Gilreath, 1954, p.230). Double displacement reaction. Redox.

Oxalate1

Chlorate

(2) The addition of sulfurous acid to this mixture produces a white precipitate that is a. insoluble in nitric acid,

The chlorate ion is reduced by sulfuric acid to the chloride ion; the latter is then precipitated as AgCl (Gilreath, 1954, p.243)

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p.140) Formation of the complex silver ammonia cation. Silver chloride ionizes to a greater extent than does silver ammonia complex cation (in an excess of NH4 OH) and, therefore, silver ions are used up in the formation of complex cation (Soine and Wilson, 1967, p.329). Caution! See Bromide. Decomposition reaction (Svehla, 1996, p.204) Decomposition reaction (Svehla, 1996, p.202)

b. but is soluble in 6 N ammonium hydroxide.

AgCl + NH4OH [Ag(NH3)2]Cl + H2O (Svehla, 1996, p.191)

Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.191)

(3) Upon ignition, chlorates yield chlorides, recognizable by appropriate tests. When sulfuric acid is added to a dry chlorate, decrepitation occurs, and a greenish yellowgas is evolved. [caution use only a small amount of chlorate for this test, and exercise extreme caution in performing it.] (1) Solutions of permanganate acidified with sulfuric acid are decolorized by hydrogen peroxide TS and by Per-manganate* sodium bisulfite TS, in the cold, and by oxalic acid TS, in hot solution. (1) With ferric chloride TS, solutions of thiocyanates yield a red color that is not destroyed by moderately concentrated mineral acids. (1) Dissolve a few mg of a tartrate salt in 2 drops of sodium metaperiodate solution (1 in 20). Add a drop of 1 N sulfuric acid, and after 5 minutes add a few drops of sulfurous acid followed by a few drops of fuchsin-sulfurous acid TS: a reddish-pink color is produced within 15 minutes. (1) To 15 mL of pyridine add a few mg of a citrate salt, dissolved or suspended in 1 mL of water, and shake. To this mixture add 5 mL of acetic anhydride, and shake: a light red color is produced.

2 KClO3 2 KCl + 3 O2 (Svehla, 1996, p.204) 3 KClO3 + H2SO4 ClO2 + ClO4 + K2SO4 + H2O + KCl (Svehla, 1996, p.202)

Crackling sound (Svehla, 1996, p.202) Orange-yellow solution with greenishyellow fumes (Svehla, 1996, p.202)

2 KMnO4 + 3 H2SO4+ 5 H2 O2 K2 SO4 + 2 MnSO4 + 8 H2 O + 5 O2 (Soine & Wilson, 1967, p.286) 5 NaHSO3 + 2 KMnO4 + 3 H2 SO4 K2SO4 + 2 MnSO4 + 5 NaHSO4 + 3 H2O (Soine & Wilson, 1967, p.287) 5 H2C2 O4 2 H2O + 2 KMnO4 + 3 H2SO4 K2 SO4 + 2 MnSO4 + 18 H2 O + 10 CO2 (Soine & Wilson, 1967, p.287) 3 KSCN + FeCl3 Fe(SCN)3 + 3 KCl (Svehla, 1996, p.184) 6 KSCN + FeCl3 K3[Fe(CNS)6] + 3 KCl (Gilreath, 1954, p.239)

Purple solution becomes colorless with bubbling (Soine & Wilson, 1967, p.286) Purple solution becomes colorless (Soine & Wilson, 1967, p.287) Purple solution becomes colorless with bubbling (Soine & Wilson, 1967, p.287) Blood-red solution

Redox.

Redox. Redox. Double displacement reaction. Complexation (Gilreath, 1954, p.239)

Thiocyanate4

Tartrate*

Reddish-pink solution within 15 minutes (USP CI, 2006, p.141)

Citrate* Fluoride1 Formate* Hexafluorosilicate* Perchlorate* Bromate* Hexacyanoferrat e (II)3 Hexacyanoferrate (III)3 Class B (1) Sulfate2

Light red solution (USP CI, 2006, p.140)

No official ID test

Precipitation Reactions (1)With barium chloride TS, solutions of sulfates yield a white precipitate that is

BaCl2 + H2 SO4 BaSO4 + 2 HCl (Svehla, 1996, p. 145)

Heavy, white precipitate (Svehla, 1996, p. 145)

Double displacement precipitation reaction.

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a. insoluble in hydrochloric acid and nitric acid,

BaSO4 + HCl no reaction BaSO4 + HNO3 no reaction (Svehla, 1996, p. 145) (CH3COO)2Pb + H2SO4 PbSO4 + 2 CH3COOH (Soine and Wilson, 1967, p.157) PbSO4 + 2 CH3COONH4 (CH3 COO)2Pb + (NH4)SO4 H2SO4 + HCl no reaction

No dissolution of precipitate; white precipitate persists (Svehla, 1996, p. 145) White precipitate (Soine and Wilson, 1967, p.157) Dissolution of white precipitate forming a clear, colorless solution No precipitate (USP CI, 2006, p.141)

(2) With lead acetate TS, neutral solutions of sulfates yield a white precipitate that is a. soluble in ammonium acetate TS. (3) Hydrochloric acid produces no precipitate when added to solutions of sulfates (distinction form thiosulfates). [Note Where the monograph specifies the identification test for phosphate, use the tests for orthophosphates, unless the instructions specify the use of pyrophosphate tests or indicate that the product to be ignited before performing the test.] (1) With silver nitrate TS, neutral solutions of orthophosphates yield a yellow precipitate [p.141], that is a. soluble in 2 N nitric acid and

The solubility of very small crystals is greater than that of larger ones with pronounced effect in hard crystals, like BaSO4, due to surface energy (Gilreath, 1954, p.96). Double displacement precipitation reaction. Double displacement reaction.

Phosphate1

Na2 HPO4 + 3 AgNO3 Ag3 PO4 + 2 NaNO3 + HNO3 (Svehla, 1996, p.219) Ag3 PO4 + 2 HNO3 AgH2PO4 + 2 AgNO3 (Svehla, 1996, p.219)

Yellow precipitate (Svehla, 1996, p.219) Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.219)

Double displacement precipitation reaction. Double displacement reaction. Formation of soluble complex. ! The solution obtained dissolving in ammonia should be discarded quickly to avoid explosion or acidified quickly with 2 M nitric acid and disposed of. Otherwise, when set aside, a precipitate of silver nitride Ag3N (fulminating silver) is formed slowly, which explodes readily even in a wet form (Svehla, 1996, p.72). Mo3O10 group replaces each oxygen atom in the phosphate. Commercial ammonium molybdate, a heptamolybdate, (NH4)6Mo7 O244H2O (Svehla, 1996, p.220). Phosphates yield the precipitate in the cold or upon gentle warming. Distinction from arsenate wherein the yellow, crystalline precipitate is formed upon boiling, and from arsenite, where no precipitate forms (Svehla, 1996, p.95).

b. in 6 N ammonium hydroxide.

Ag3 PO4 + 6 NH4 OH [Ag(NH3)2]3PO4 + 6 H2O (Svehla, 1996, p.219)

Dissolution of precipitate forming a clear, colorless solution (Svehla, 1996, p.219)

Ortho-phosphate

(2) With ammonium molybdate TS, acidified solutions of orthophosphates yield a yellow precipitate that is

Na2 HPO4 + 12 (NH4)2MoO4 + 23 HNO3 (NH4)3[P(Mo3 O10)4] + 12 H2 O + 2 NaNO3 (Svehla, 1996, p.219)

Yellow, crystalline precipitate Svehla, 1996, p.219)

a. soluble in 6 N ammonium hydroxide. This precipitate may be slow to form. (1)With silver nitrate TS, pyrophosphates obtained by ignition yield a white precipitate that is Pyro-phosphate P2O72a. soluble in 2 N nitric acid and b. in 6 N ammonium hydroxide. (2) With ammonium molybdate TS, a yellow precipitate that is

(NH4)3[P(Mo3 O10)4] + NH4OH dissolution of precipitate Na2 P2O7 + AgNO3 Ag4P2 O7 + NaNO3 Ag4 P2O7 + 4 HNO3 H4 P2O7 + 4 AgNO3 Ag4 P2O7 + 8 NH4OH [Ag(NH3)2]4P2O7 + 8 H2O

Dissolution of precipitate forming a solution (USP CI, 2006, p.141) White precipitate (USP CI, 2006, p.141) Dissolution of precipitate forming a solution (USP CI, 2006, p.141) Dissolution of precipitate forming a solution (USP CI, 2006, p.141) Yellow precipitate (USP CI, 2006, p.141)

Double displacement precipitation reaction Double displacement reaction Formation of soluble complex. !

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a. soluble in 6 N ammonium hydroxide is formed. (1) In moderately dilute solutions of salicylates, ferric chloride TS produces a violet color. (2) The addition of acids to moderately concentrated solutions of salicylates produces a white, crystalline precipitate of salicylic acid that melts between 158 and 161C. (1) When strongly heated, hypophosphites evolve spontaneously flammable phosphine. (2) Hypophosphites in solution yield a white precipitate with mercuric chloride TS. This precipitate becomes gray when an excess of hypophosphite is present. (3) Solution of hypophosphites, acidified with sulfuric acid, and warmed with cupric sulfate TS yield a red precipitate. 4 NaH2 PO2 Na4 P2O7 + 2 PH3 + H2O (Svehla, 1996, p.224) HPH2O2 + 4 HgCl2 + 2 H2O 2 Hg2Cl2 + H3PO4 + 4 HCl (Svehla, 1996, p.224) 2 Hg2Cl2 + HPH2O2 + 2 H2O 4 Hg + H3 PO4 + 4 HCl (Svehla, 1996, p.224) 2 CuSO4 + 2 HPH2O2 + 4 H2 O 2 H3PO4 + Cu2 H2 + 2 H2SO4 + H2 (Soine and Wilson, 1967, p.138) 4 CuSO4 + 3 HPH2O2 + 6 H2 O 3 H3PO4 + 4 CuH + 4 H2SO4 (Svehla, 1996, p.224) 3 C6H5 COOK + 2 FeCl3 + 3 H2 O (C6 H5COO)3Fe Fe(OH)3 + 3 KCl + 3HCl (Svehla, 1996, p.242) 2 C6H5 COOK + H2 SO4 2 C6 H5COOH + K2SO4 (Svehla, 1996, p.242)

Dissolution of precipitate forming a solution (USP CI, 2006, p.141) Violet-red solution (Svehla, 1996, p.241)

Salicylate*

White, crystalline precipitate (Svehla, 1996, p.241)

Hypo-phosphite*

Colorless, extremely toxic, smells slightly of garlic or bad fish, highly reactive (Lee, 1997, p.481) White precipitate (Svehla, 1996, p.224) White precipitate turned gray (Svehla, 1996, p.224) Red precipitate; bubbling (Soine and Wilson, 1967, p.138) No precipitate in the cold, but on warming red precipitate is formed (Svehla, 1996, p.224) Buff (pale yellowish beige)-colored precipitate (Svehla, 1996, p.242) or salmon-colored precipitate (USP CI, 2006, p.139) White, crystalline precipitate (Svehla, 1996, p.242)

Disproportionation reaction Redox Mercurous salts are easily reduced to free mercury (Soine and Wilson, 1967, p.138) Redox.

Redox.

(1) In neutral solutions, benzoates yield a salmoncolored precipitate with ferric chloride TS Benzoate* (2) In moderately concentrated solutions, benzoates yield a precipitate of benzoic acid upon acidification with 2 N sulfuric acid. This precipitate is readily soluble in ethyl ether.

Substitution reaction.

Succinate* Arsenate1 Chromate2 Silicate* Peroxodisulphate* No official ID tests Phosphite* Arsenite1 Dichromate Hexaflurosilicate* Class B (2) Oxidation/ reduction in solution Permanganate* Manganate* Chromate2 No official ID test Dichromate* Other unclassified common anions

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(1) When solutions of lactates are acidified with sulfuric acid, potassium permanganate TS is added, and the mixture is heated, acetaldehyde is evolved. Lactate* This can be detected by allowing the vapor to come into contact with a filter paper that has been moistened with a freshly prepared mixture of equal volumes of 20% aqueous morpholine and sodium nitroferricyanide TS: a blue color is produced. 2 K2Cr2 O7 + 2 H2SO4 + 2 H2O2 2 CrO5 + H2 Cr2O7 + 2 K2SO4 + H2O (Svhela, 1996, p.226). (1) Solutions of peroxides slightly acidified with sulfuric acid yield a deep blue color upon the addition of potassium dichromate TS. Peroxide* H2SO4 H2Cr2O7 H2O + 2 CrO3 (Parks et al, 1949, p.138) K2Cr2O7 + H2SO4 H2 Cr2O7 + K2SO4 H2Cr2O7 + H2O2 HOCrO2OOCrO2OH + H2O (Soine and Wilson, 1967, p.53) 4 CrO5 + 6 H2SO4 2 Cr2(SO4)3 + 7 O2 + 6 H2O (Svehla, 1996, p.125)

Odor resembling that of bitter almond (Gennaro, 2000, p.1020)

Paper turns blue (USP CI, 2006, p.140). Chromium pentoxide test; (Svehla, 1996, p. 245). Dichromic acid, with more sulfuric acid, is dehydrated to chromium trioxide (Parks et al, 1949, p.138) Perchromic acid (Soine and Wilson, 1967, p.53). Formation of beautiful blue in the upper organic layer (Svehla, 1996, p.245) and green lower aqueous layer, with bubbling (Svehla, 1996, p.125). Chromium pentoxide (chromium peroxide, peroxochromic acid) test; Decomposition of CrO5 (Svehla, 1996, p.125).

Evanescent blue color (Soine and Wilson, 1967, p.53) then a green solution (Svhela, 1996, p.226)

On shaking the mixture with an equal volume of ethyl ether and allowing the liquids to separate, the blue color is found in the ethyl ether layer.
Acetate Carbonate (acids) p. 139 ; References:

Carbonate (phenolphthalein) Phosphate (o-, yellow ppt) p. 140 ;

Phosphate (soluble) Zinc p.141

GENNARO, A. R., 2000. Remington: The Science and Practice of Pharmacy. 20 ed. Philadelphia: Lippincott Williams & Wilkins, 402, 1020, 1032, 1212. GILREATH, E. S., 1954. Qualitative Analysis Using Semimicro Methods. Quezon City: Ken, Inc., 96, 186-7, 194, 198-9, 210, 217, 225, 230, 239. HOLZCLAW, H. F., Jr., and W. R. ROBINSON, 1988. College Chemistry With Qualitative Analysis. 8 ed. Massachusetts: D. C. Heath and Company, 375, 667, 812, 819, 833, 842, 931, 941, 943, 945, 962, 994. LEE, J. D., 1996. Concise Inorganic Chemistry. 5 ed. London: Chapman & Hall, 287-8, 382, 481, 501, 728, 825, 827, 846. MOST, C. F., Jr., 1988. Experimental Organic Chemistry. New York: John Wiley & Sons, Inc., 519. PARKS, L. M., JANNKE, P. J., and L. E. HARRIS, 1949. Inorganic Chemistry in Pharmacy. Philadelphia: J. B. Lippincott Compnay, 57, 138, 144, 149, 183, 209, 941. PETRUCCI, R. H., and W. S. HARWOOD, 1997. General Chemistry: Principles and Modern Applications. 7 ed. New Jersey: Prentice-Hall, Inc., 766. SHRINER, R. L., HERMANN, C. K. F., MORILL, T. C., CURTIN, D. Y., and, R. C. FUSON, 1998. The Systematic Identification of Organic Compounds. 7 ed. New York: John Wiley & Sons, Inc., 88. SOINE, T. O., and C. O. WILSON, 1967. Rogers Inorganic Pharmaceutical Chemistry. 8 ed. Philadelphia: Lea & Febiger, 62, 76, 82, 96, 128, 138, 151, 157, 193, 210, 220, 238, 243, 250, 286-7, 302, 318-20, 329, 355-6, 375, 407-8, 424-7, 451, 515, 545, 547, 551, 575, 605-6, 633, 672. SVEHLA, G., 1996. Vogels Qualitative Inorganic Analysis. 7 ed. England: Longman Group Limited, 7, 64-5, 68, 70, 72-3, 78, 80, 84, 95, 98, 100, 110-1, 113-6, 118-20, 125, 129-30, 137, 140, 145, 147, 150, 153, 156, 163-4, 168, 171, 173-4, 177, 184, 191, 193-4, 196, 199, 200, 202-4, 209, 219-20, 224-6, 230-1, 234-5, 241-242, 311. UNITED STATES PHARMACOPEIAL CONVENTION, 2006. United States Pharmacopeia 30 Revision and the National Formulary 25 Edition. Asian Edition. Maryland: USPC, 139-141.
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