36 Kalyani Unified Chemistry (Inorganic Part.) ammonia upon heating but can be reformed by treatment of anhydrous cobalt (II) chloride with ammonia vapour, that is, by increasing the pressure of ammonia. [Co(NHg)6ICl; A, CoCl, + 6NH3 Similarly, reduction in pressure above causes loss of volatile components. 2. Concentration factors. There are many complexes which may exist in water solution only in the presence of a high concentration of the coordinating particles. The reason is that in such cases, the water molecules apparently are having greater coordinating tendencies than the molecules or ions originally present. For example, the yellow species of [CuCl,]*- complexes exists in the solid state but when dissolved in water, a pale blue hydrate of copper (II) ion gets formed which on addition of excess of chloride ion (in the form of HCl, LiCl or other very soluble) regenerates the yellow complex. 2xH,0 [CuCl,?- === [Cu(H,0),]?* ‘Yellow 4cl- Blue Similarly, the blue complex of cobaltous ion of the type [Co (CNS),4]?-_ undergoes the change as given as follows : HO [Co(CNS),}- <== [Co(H,0).]?* Blue 4CNS- Pink Another analogous competition between coordinating particles involves the CNS- ion and the F- ion (in place of water) for the Fe*3 ion. The things will become clear in the following equation; in the presence of excess of thiocyanate ions the complex is dark-reddish brown, whereas in the presence of excess of fluoride ions, the complex is colourless. oF [Fe(CNS),]3- === [FeF,]3- Dark-reddish uswn 6CNS- Colourless 3. Effect of Central Ion. It is a special property of d- electrons, that is, of transition metals that they form complexes. The various factors are : (a) Jonic size. The smaller an ion, the greater its electrical field, and in general, the more stable its complexes. The following stability constants for hydroxide complexes of the alkaline-earths illustrate the point : BeOH* MgOH* CaOH* BaOH* Stability Constant 107 120 30 4 (6) Ionic charge. For ions of equal size, those with higher charge exert the stronger field and form more stable complexes. The ferricyanide ion (logig K = 31.0), for example, is more stable than the ferrocyan'de (logiy K = 8.3) and cobalt (II) complexes are more stable than those of the cobalt (III). Combination of factors (a) and (b) shows that a large charge/radius leads to stable complexes. 4. Effect of the Ligands. Common ligands possess lone pairs of electrons whereby they serve as donors. Electropositive groups are immediately ruled out as ligands. Ligands containing electronegative atoms such as carbon, nitrogen, oxygen, sulphur or halogens are most useful donors. Some of the characteristics of the ligands include factors such as :