186

Exercise 13

thiosulphate solution to the other test tube. Note the changes that occur and write the equation of the reaction. What is the practical significance of this last reaction? 2. Detection of the Cupric and the Silver Ion. Receive from the instructor a test solution containing one of these ions. By means of the maximum number of the reactions you have studied, prove the presence of one of these ions in the solution. 3. Electrolysis. Clean the surface of a copper plate with sandpaper until it shines, immerse it for 3-4 minutes in a 15% solution of nitric acid, rinsing it afterwards thoroughly with water under the tap. Assemble the apparatus shown in Fig. 69. Into the electrolytic cell pour an amount of the solution sufficient to cover three-quarters of the plates. Lower the electrodes into the solution and adjust the rheostat to maximum resistance. Close the circuit by means of the key, note the time of the beginning of the experiment (start the stop watch), and reduce the resistance so as to bring the voltage up to 1.2- 1.4 V. .Read the current intensity on the ammeter. Exactly 15 minutes later break the circuit and rinse the iron plate with water. The copper coat ing is a compact reddish layer without lustre. Measure the surface area of the plate. Knowing the current intensity and the duration of -electrolysis, calculate the thickness of the coating (the density of copper is 8.9 g/cu cm).

Exercise 22
COMPLEX COMPOUNDS

SUBJECTS FOR STUDY

Basic principles of the Coordination Theory; central atom; coordination number; ligands; the inner and the outer coordination sphere. . Electrolytic properties of complex compounds and their conductivity; dissoci^ation of a complex ion and the instability constant of complex compounds; complex ions in exchange reactions, and complex ions in redox reactions.

The so-called complex compounds contain more elaborate groups of ions, with properties differing from those of elementary ions, e. g.:
+3 43 *^2

Nas [Co (N02)61 K(Co (NH3)2C14] [Zn (NH8),1 (OH), [Pt (NH3)4C121C12 ' A complex compound has a central atom,, or complex-forming ion, with a characteristic valence (charge) and a coordination number, which indicates how many groups, atoms, ions, or molecules are linked to the complex former in the inner sphere. With these ligands*

* This term has superseded the earlier term addend. * The yellow precipitate formed is sulphur produced by a side reaction of oxidation.

Complex Compounds

187

the complex former constitutes what is known as a complex ion, whose charge is the algebraic sum of the charges of the complex former and the ligands. If the complex ion has a negative charge, the outer sphere consists of positive ions, and vice versa. For example: K' [Au (CN)2]'
complex anion

[CU (NH3)4fCi;
. complex cation

To write the formula of a complex compound, it is necessary to know the valence (charge) of the complex former and the ligands, as well as the coordination number. The following are the coordination numbers of the most important complex formers:
4
+1 +1 Ag,

Au

+2 Cu, +2 Pt, +2 Pb,

+ 2 Hg + 2 Co, +3 Au +3 B +3 Fe, +2 Zn,

+3 Co, +4 Pt, +2 Cd,

+2 Ni, +3 Cr, +4 Sn,

-t2 Fe +2 M n +3 A1

These are the most widespread coordination numbers of central atoms. Less frequent coordination numbers are 3, 8, and 12. One and the same complex former may have several different coordination +2 numbers: for instance, Al+S, Co+2, and Zn are known to have the coordination numbers 4 and 6. Both electrically neutral molecules (H20, NH3, NO, etc.) and negative ions (0, OH-, N02~, CN_, Cl", Br~, I", C03~", etc.) can be ligands.

Example in Writing the Formula of a Complex Compound. Write the formula of a +3 + complex compound consisting of the ions Fe , CN^.and K . Since the positive ions + K cannot be part of the inner sphere, the CN ions form the inner coordination +S sphere around the Fe ion. The latter ion has the coordination number 6; the formula is therefore K3[Fe(CN)6].
The most important complex compounds with neutral ligands are the

ammoniates, e. g., ICo(NH3)8]C13, and aquocomplexes, e. g., [Cr(H20)6]Cl3; the

latter group includes the so-called crystalline hydrates. Complex compounds in which negatively charged acid radicals are grouped around the central atom are known as acid complexes. e. g., K3[Co(N02)6]. In an aqueous solution complex compounds dissociate into a complex ion and the ions that make up the outer sphere. For example: [Cu (NH3)J Na3 [Co (N02)8]

S04^ [Cu (NH ) ]" + sol

3 4

^ 3Na + [Co (N02)a]'"

188

Exercise 19

In exchange reactions complex ions pass from one compound to another without any change in their composition: 2Cu + 2SOI + 4K' + [Fe (CN)er = Cu2 [Fe (CN)6] + 4K' + 2SOI In solution complex ions dissociate to a certain degree: [Cu (NH3)4]^tCu + 4NH3 For this case of equilibrium we may write:
[Cu] [NH,]
K

[[Cu (NH3)4]"]

The quantity K (the ratio of the product of the concentrations of the particles into which the complex ion dissociates to the concentration of the complex ion) is called the instability constant of the complex ion. The greater this constant, the less stable the complex. [Ag(NH3)ar^Ag+2NH#

K = 6.8- 1CH [Ag (CN)ar ^ Ag- + 2CN' K = 1 10-21

It is evident from these figures that the ammoniate of silver is less stable a complex than the cyanide. The instability constants of some complex ions are listed in Table XIV (p. 335). A decrease in the concentration of one of the components of a complex can cause its destruction.Let us take solutions of two nickel salts: NiS04 and [Ni(NH3)6]S04. Both solutions are in a state of equilibrium: NiS04 Ni" + SOI [Ni (NH3)6]S04 ^ [Ni (NH3)6] + SOI

If

Ni + 6NH8 The addition of a solution of NaOH causes the precipitation of Ni(OH)2 in the first solution, but no precipitation in the second. For a precipitate to be formed, it is necessary that the product of the 2 concentrations [Ni]* [OH'J be greater than the solubility product SPpji(on)i. Although the complex ion [Ni(NH3)6] does dissociate into Ni ions and NH3 molecules, the extent to which it does this is so small that the concentration [Ni] is insufficient for the SP value to be reached and no precipitate is therefore formed. The addition of ammonium sulphide to the NiS04 and[Ni(NH3)6]S04 solutions causes a precipitate of NiS to be formed in both cases. Nickel sulphide is much less soluble (SPnis = 1 -4* 1024) than is nickel hydroxide (SPnuoh), 1*6-1014 ). The concentration of NT ions even in the complex salt solution is sufficient for the SPnis value to be reached. As the S" ions bind the Ni ions, there is a shift in the equilibrium in the system [Ni(NH3)6]"iNi -f 6NH3 towards the dissociation of the complex ion, which leads to the complete destruction of the complex ion. Redox reactions of complex compounds involve either a change in the charge of the complex former without any substantial disturbance in the composition of the complex (example l)or the complete destruction of the complex with the formation of oxidation products of simpler composition (example 2):

1 -

2e~

Complex Compounds

189

(1) 2K4 (Fe (CN)J + Cl2 = 2K3 IFe (CN),] + 2KC1 leI 8e- I I -----
1+2 -1 -''I +3

+2

+3

-1

(2) 2K2 [Ni (CN)*1 + 9Br2 + 6KOH = 2Ni (OH)3-| 8CNBr + lOKBr. 2eI -* ^
+1 +2

+1

If a complex contains positive ions, which are oxidising agents, as complex formers, they can be extracted as neutral atoms by the method of reduction:

Zn + 2K [Au (CN),1 = 2Au + K2 [Zn (CN)41 The positive ions can be reduced by means of an electric current (in galvanisation, for gold- and silver-plating, etc.). The process whereby amphoteric hydroxides dissolve in solutions of alkalis is now regarded as a process of the formation of specific complex compounds called hydroxy salts, in which the complex ion consists of a central atom and hydroxyl ions in its coordination sphere. For example, when stannous hydroxide is dissolved, the process may be represented by the following equation: Sn (OH), + 2K* + 20H' = K, [Sn (OH)4l This compound is called potassium hydroxystannite.

QUESTIONS

1. Is there a difference between double and complex salts? 2. Write the coordinate formulae for the ammoniates CoCl 3-6NH8 and
CoCl8*5NH3. Why does the precipitation of the chloride ions from 1 mol of the former compound require 3 mols of silver nitrate, whereas the precipitation of the chloride ions from 1 mol of the latter requires only 2 mols?

190

Exercise 18

3. For the system in equilibrium

[Ag (NH3)21 Cl -[Ag (NH3)2] + cr

write the equations of the ionisation constant and the instability constant. Why is no AgCl precipitate formed despite the presence of Ag" and Cl' ions in the solution? Why does the addition of nitric acid to the solution cause the precipitation of AgCl? 4. Why does the treatment of a CdCl2 solution with an alkali produce a Cd(OH)2 precipitate, while the treatment of a [CdiNH^elCl* solution does not? 5. Write the equations for the oxidation of yellow prussiate of potash K4[Fe(CN)6] by hydrogen peroxide in an acid solution and for the oxidation of the complex compound K4[Co(CN)6l by the oxygen of the air in a neutral solution. 6. Write the equation for the reaction of the formation of potassium hydroxyaluminate from aluminium hydroxide.

Problems
1. A certain amount of metallic zinc reacts with a solution of K[Au(CN) 2] io yield 7.89 g of metallic gold. The amount of 10%HCl needed to dissolve the same amount of metallic zinc is 14.6 g. Calculate the equivalent of the gold. 2. A complex compound contains Co"\ NH3, and Cl'. The precipitation of the Cl' from 11.67 g of this salt requires 8.5 g of silver nitrate. When the same amount of the complex salt was broken down, the yield of ammonia was 4.48 litres (reduced to N. T. P.). The molecular weight of the salt is 233.3. Write the coordinate formula of the complex compound. 3. What amount of a 5% solution of (NH4)2S is needed for the complete precipitation of the copper as sulphide from 120 ml of an 0.1 M solution of [Cu(NH3)4] S04? 4. The oxidation of a 3% solution of H202 in an alkaline medium by potassium ferricyanide K3[Fe(CN)6] yields 560 ml of 02, measured at N. T. P. Calculate the amounts of 3% H202, solid K3[Fe(CN)6], and 20% KOH that were used up. 5. It is necessary to prepare 80 litres of an 8% solution (relative density 1.043) of K3[Fe(CN)6] by diluting an 18% solution (relative density 1.10). Calculate the amounts of water and of the initial solution that have to be mixed. 6. Determine the molarity of a solution of [Ag(NH3)2]Cl if 4.4 ml of HN03 (titre 0.063) is used to bind the ammonia contained in 20 ml of the solution. 7. What will be the boiling point of 0.1 M K3[Fe(CN)6], its relative density being and its degree of ionisation 65%? ^ 8. Calculate the osmotic pressure at 0 of 8% K3[Fe(CN)fl], its relative density being 1.043 and a being 62%. ' 9. For how long is it necessary to pass a 2-ampere electric current through a K[Ag(CN)2] solution to deposit 0.24 g of metallic silver? ^ 10. A 5-ampere current is passed for 20 minutes through a [Ni(NH3)6]S04 solution. Calculate by how many grams the weight of the cathode increases. LABORATORY WORK

Apparatus and materials: test tubes and rack; funnel; 2 watch glasses; filter paper;
wash bottle; litmus paper; splints; 2 N KOH; N BaCl2; N FeCl3; 2 N (NH4)2S; 0.5 N KSCN. 2N HN03; 0.5 N solution of aluminium potassium sulphate; 2 NKOH;

Complex Compounds

19f

0. 4 N solution of sodium bitartrate; solution of sodium cobaltinitrate; saturated and' 0. 1 N solutions of silver nitrate; saturated solution of CoCl2; saturated solution of ammonium rhodanate; saturated solution of potassium iodide; 0.5 N ZnCl 2; 0.5 N KC1; 0.5 N CuS04; 10% ammonia solution; 3% H202; N solutions of potassium ferro* and ferricyanide; N FeS04, and chlorine water. Preparation of Sodium Cobaltinitrate. Dissolve 50 g of CoCl2-6H,20, with gentle heating, in 50 ml of water, cool the solution, and mix it with a solution of 150 g of sodium nitrite in 500 ml of water. Add 50 ml of 5% CH 3COOH, while stirring. When the precipitate has settled, pour oS the liquid into reagent bottles.

1. Ions of a Double Salt. Pour 2 ml of a KA1(S04)2 solution into- each of three test tubes; add a sodium bitartrate solution (see Exercise 20, experiment 5) to the first, a few drops of an NaOH solution to the second, and a barium salt solution to the third. Write ionic equations for all three reactions. What ions may be assumed to be present, in the initial solution on the basis of these, reactions? Write the equation for the electrolytic dissociation of KA1(S04)2. 2. Ions of a Complex Salt, (a) Pour 2 ml of a FeCl3 solution into each of two test tubes; add a solution of (NH4)2S to one and a K.SCN solution to the other. What is formed? Write ionic equations of the reactions. What ion may be assumed to be present in the FeCl3 solution on the basis of the reactions with the S" and SCN" ions? (b) Carry out analogous reactions, substituting a K3[Fe(CN)6f solution for the FeCl3 solution. Is a black precipitate * formed? Does a red colouration appear? Are there Fe ions in the K3[Fe(CN)6l solution? Write the equation for the electrolytic dissociation of K 3[Fe(CN)6], Prove experimentally that the solution of this salt contains potassium ions (see Exercise 20, experiment 5). What are complex salts? Can a sharp dividing line be drawn between double and complex salts? Write- equations of electrolytic dissociation for the salts:
NH4Cr(S04)2 [Cu(NH3)4]Cl2 K2iPtCl6]

3. Compounds with a Complex Negative Ion. (a) Place a drop of a* saturated solution of silver nitrate on a watch glass and add a saturated solution of potassium iodide io it by drops until the precipitate formed dissolves. Write the equations of the reactions that have taken place. Keep the solution for experiment 6. (b) Place 3-4 drops of concentrated solutions of CoCl2 and NH4SCN on a watch glass. The solution acquires the blue colour typical of [Co(SCN) 4]" ions. Write the equation of the reaction. ':Keep the solution for experiment 6. ~ (c) Add an alkali solution by drops to a zinc salt solution until a white precipitate is formed. Write the equation of the reaction. Add

192

Exercise 22

-excess alkali to the precipitate. The precipitate dissolves owing to the formation of hydroxyzincate. Write the equation of the reaction. 4. Compounds with a Complex Positive Ion. Prepare the precipitates of AgCl and Cu(OH)2 by exchange reactions, pour off the liquid from the precipitates when they have settled, and add excess ammonia solution to the precipitates. Write the equations of the reactions whereby the precipitates are dissolved. Note the colour of the solutions of the complex compounds. Keep the ammonia solutions for experiment 6. 5. Complex Compounds in Exchange Reactions, (a) Add a solution of yellow prussiate of potash to an equal volume of a dilute, acidified solution of FeCla. What is formed? Write the equation of the reaction that takes place. (b) Add a Na3[Co(N02)6] solution to a KC1 solution. A yellow crystalline precipitate of K2Na [Co(N02)6] is formed. Write the equation of the reaction. 6. Destruction of Complex Ions, (a) Dilute with water (by drops) the complex compound solutions on watch glasses left over from experiment 3. Observe the changes that take place. Write the equations for the electrolytic dissociation of the complex ions.How is the balance shifted by the addition of water? How does the concentration of the solution affect the stability of complex compounds? (b) Add nitric acid to the solution of silver diamminochloride [Ag(NH3)2lCl from experiment 4 until the solution changes the colour of litmus paper. A white precipitate of silver chloride is formed. Write the equation of the electrolytic dissociation of the complex compound and explain the role of nitric acid. (c) Divide the blue solution of cupric tetramminohydroxide left over from experiment 4 into two parts. Add a sodium hydroxide solution to one part and an ammonium sulphide solution to the other. Explain why a precipitate is formed in one case only. 7. Complex Compounds in Redox Reactions, (a) Mix 2 ml of a hydrogen peroxide solution in a test tube with an equal volume of a potassium hydroxide solution; add 2 ml of a K3[Fe(CN)6] solution. -Confirm by a glowing splint that oxygen is evolved. Write the equation of the reaction that has taken place. (b) Test the effect of a newly prepared FeS04 solution on potassium ferrocyanide and ferricyanide. Which of these salts produces a blue colouration? Add a few drops of potassium ferrocyanide to 3 -4 ml of chlorine water and boil the solution thoroughly (to remove the excess chlorine). Add FeS04 to the resulting solution. What is observed? Write the equation for the oxidation of potassium ferrocyanide by chlorine.

194

Exercise 13

The oxides of the metals are for practical purposes prepared by the thermal decomposition of the carbonates (Mg and Ca) or the nitrates (Sr and Ba): CaC03i CaO -f> COa 2Ba(NOs)2 = 2BaO + 4N02 + 02 The hydroxides of the group may be prepared by treating the oxides with water; the hydroxides of magnesium and beryllium may also be prepared by exchange reactions of salts with alkalis, thanks to the poor solubility of these hydroxides in water. The oxides and hydroxides become increasingly alkaline with the rise in the +2 radius of the Me ion; the hydroxide corresponding to Be+2, the ion with the smallest radius, is amphoteric. In the laboratory it is customary in most cases to use a solution of Ca(OH) 2, known as lime water, or a suspension of solid calcium hydroxide in a saturated solution, known as lime milk, and a solution of Ba(OH)2, known as baryta water. The volatile salts of calcium, strontium, and barium impart a brick red, carmine, and yellowish green colour respectively to a nonlumino- us flame of the Bunsen burner. Among the insoluble salts, mention should be made of the carbonates MeC03 and the ortho-phosphates Me3(P04)2. The solubility of the sulphates MeS04 decreases from Be to Ra: the sulphates of Sr, Ba, and Ra are practically insoluble, CaS04 is somewhat soluble, and the sulphates of Be and Mg are highly soluble. Barium chromate BaCr04, unlike strontium chromate, which dissolves in acetic acid, dissolves in hydrochloric acid. The chromates have a yellow colour. Treatment of the carbonates with an aqueous solution of carbon dioxide causes them to dissolve with the formation of bicarbonates: CaC03 + H20 + C02 = Ca(HC03)2 Natural water with large amounts of calcium and magnesium salts in solution is known as hard water. Soft water contains relatively small amounts of dissolved salts. According to the Standards in operation in the U.S.S.R., the hardness of water is expressed in the number of milligram-equivalents of Ca" or Mg" ions in 1 litre of water. Water with a hardness of less than 4 mg-equiv./lit is called soft; water with a hardness of from 4 to 8 mg-equiv./lit is called medium; from 8 to 12, hard, and above 12, very hard. One mg-equiv. of Ca" corresponds to 20.04 mg; 1 mg-equiv. of Mg", to 12.16 mg. The presence of Ca(HC03)2 and Mg(HC03)2 in natural water is responsible for what is known as temporary (or removable) hardness. The chlorides and sulphides of calcium and magnesium are the cause of what is termed the permanent hardness of water. Together, the tempo-