7. EXPERIMENTAL DETERMINATION OF STABILITY CONSTANT AND COMPOSITION OF A COMPLEX 7.1 Spectrophotometric Method [5] This method is based on Beer's law, which says that A = & 1 x ¢, where A is the optical density or absorbance, € (epsilon) is the mole extinction efficient, | is the length of the cell and ¢ is the concentration, Consider the formation of a complex given by the following reaction: tS [ML*"] M"“+L2ML™ kK; earn * iw) a The complex [ML*"] exhibits a characteristic absorption pattern depending on its composition. The wavelength at which the complex absorbs most is termed as hmax. The value of the formation constant K; can he obtained by measuring the absorbance (4) of the sample solution at the Janay Of the complex. According to the standard procedure, a known quantity of metal ion and ligand are equilibrated. Under equilibrium conditions, both metal and ligand can exist in the solution, either in the free state or complexed form, Thus, the total metal concentration [Cy] and total ligand concentration [C1] can be given as the follow [Cu] = [M*"] + [ML*"] and [C,] = [L] + [ML™" [Cu] = [M*"] + [ML**] and [C,] = [L] + [ML*] im = [Cy] — [ML**] and [L] = [C,] - [ML*’] The term ‘c’ in the Beer’s equation can be replaced by [ML*"] in this case Thus, Beer's equation can be shown as [ML**] = 4 Hence, and {t) = [eyo [me A ex] ex [cw ‘The values from these two equations enable the solution of the equation for the formation constant.7.1 Job's Method Analogous to the spectrophometric method, the Job's method also involves, the measurement of absorbance of the complex at its Aya. This method involves the preparation of several sets with constant volume and variable concentrations of the complexes. Due to this, this method is also known as the method of continuous variation. Using this method, it is possible to determine the metal-ligand ratio (composition) of a complex [1]. The standard procedure involves preparation of 10 sets of solutions of a com- plex. Different volumes of metal and ligand solutions are equilibrated in these sets in such a way that the total volume of every set remains the same. An illustration of such a set preparation is shown in Table 3: Table 3 Preparation of sets for a Job's method experiment Set No. 1 2 3 4 5 6 7 8 9 1 M*™ (ml) ofr} 2];,3 )4]5]e]7)]8]9 L (ml) wfo}s}|7fo};s]4}3}2 4a Total m) | 10 |10 | 10 10 fro Jaro | io | av | a0 Jao In each of the sets, the sam (C) of total concentration of the met: (Cus) and total concentration of the ligand (C,) remains constant (i. C= Cy + CG remains constant). The graph of the mole fraction of ligand (wf, = C,/C) against absor- bance (A) measured at the characteristic 2yax Will appear as shown Figure 3. ion The mole fraction of ligand comesponding to the maximum absorbance can be identified by equation, the absorbance is directly proportional to the concentration of the complex. Hence, this point corresponds to the composition with the trapolating the legs of the curve. From Bmaximum concentration ot the complex. Mole fraction of ligand > jure 3A plot of mole fraction of ligand —> absorbance measured at a characterist Fora complex ML,, ‘r’ represents the number of ligands per metal ion and can be mathematically equated as C,/Cy. For example, if the complex is represented bya formula ML, the value of ‘1’ is 1, and it is said that the metal ligand ratio in this case is 1:1. In such a case, the concentration of the complex will be at a maximum in set number six, which contains an equal volume of metal and ligand solutions. The mole fraction of ligand comesponding to this set can give the value of ‘n’ using the following equation: For set number 6, mf, = C./C = 5/10 = 0.5 Thus, inf 05 "Tomi 1-05 Even though Job’s method is a user-friendly method, it is necessary to make sure before using this method that the metal and ligand do not make complexes of more than one composition. Under certain circumstances, it becomes very difficult to create several sets with a constant volume. The application of Job's method is not possible in such cases.7.2 Mole Ratio Method This method is a similar, yet simpler, version of the Job’s method. The difference between the two methods is that in the molar ratio method, the total analytical concentration of metal/ligand is kept constant instead of the sum of ligand and metal concentration. The absorbance is measured at a wavelength, where the complex absorbs strongly but the ligands and metal ion do not. A plot between absorbance versus ligand to the metal con- red as shown in Figure 4. Extrapolating (C/Cyy) gives centration ratio (C,/Cu) is prepa the straight line portions until they cross, the value of R the ratio of ligand to the metal ion in the complex. Hence, a formula of the complex ML, can be easily determined. Limiting Logarithmic Method Theory ‘The limiting logarithmic method consists in measuring the optical densities of solutions of metal (M) jon and ligand (L) in which the concentrations of the {wo species are varied in tur at a constant total concentration. It is assumned that Beer's law is applied, ie, the optical density atthe absorption peak is proportional to the concentration of the complex. For the reaction mM+iL > Maly ‘The stability constant. K is given by (M, Li} iM" Lt (On taking logarithms, we get log{MaLJ= mlog(M] + HlogiL] + log K 5) “The values of m, { and K may be fourd by plotting the logarithms of the optical densities of wo sets of solutions versus composition. (One with constant metal and variable ligand concentra- tion, and Gi) The other with constant tigand and variable metat concentration (Fig. 12.60). ‘The slope of the curve in case (i) yields “I” while in case of (ii) “mis obtained. From these values of “I” and “mand equation (5), ‘values of K and the composition of the complex can be calculated. Limitations (The method is onty suitable at iow conecntrations. Gi) The value of sibility consiant obtained by the method is higher than that given in the literature. Log (M) oF Log (L) = 0 “Wy ‘Log Optical Density,higher than that given in the literature, 3. Molar Rarlo Method : This method is vary simple as com- pared to the continuous variation method. The difference between two ‘methods is that in the molar ratio method, the total analytical concentra- tion of metal (or ligand) is held constant rather than the sum of ligand and metal concentration. Optical density is measured at such a wavelenght of light at which complex absorbs strongly whereas the ligands and metal ion do not. ‘Then draw a graph between absorbance, ie., optical density versus ligand to the metal concentrations é} Extrapolate the straight line Portions until they cross. At this point, the value of Eels the ratio of ligand to the metal ion in the complex (Fig. 12.61). Hence, formula of the complex MXp can be easily determined. 4, Matching Absorbance Method : This method is quite useful for the determination of stability constants. This method involves the following steps : (The absorbance of two solutions having different metal to ligand Log (M) or Log ) Fig. 12.60, Lntioglogerthmic ratios are measured at a wavelength where ony the complex absorbs strongly, and the ligand and metal ion do not (i) Then di ‘two solutions becomes the samme. (Git) Let the concentration of metal ard ligand in solution (1) be Cut ‘the solution (2) Cy2 and Cya are the corresponding quantities. (iv) For! : I complex, we have (Mi) = Ca —(MXI (Xil= Gu —(MXh, (MG] = Car — (MX]2 (1) = C2 —([MXh lute the solution of higher absorbance to such an extent until the absorbance of the and Cx, respectively. For ‘When the avssorbance of the two solutions becomes equal then (MX]i=(MXla= Cs where Cr is some unknowa concentration. (¥) The stability constant K can be calculated-farm the stcbility constant expression which con- tains Cs and K as unknown by eliminating Cs. Thus, x= 20), (MG) Tae ~ (Mab o cs cs Cai=C) C51=C5) ~ (Cur= C8) (Co= C9 (CusCxi) ~ (Cuea) (Cm + Cx) (Cua + Cx) ‘Thus, the siability constant can be easily determined and c= © (5) Bjerrum Method : Bjerrum determined formation constants of metal complexes and chelate compounds in aqueous solutions. Bjerrum described the stepwise formation of series of metal complexes of the type ML, MLz.... . .MLy which are defined by equations (6) to (8). M+L—> ML [MLa} ML+L > Min Ke= ity \ = Mb) _ Mii tL Mi Ke= ia dit] © o ~®of the type ML."ML..... ML, which are defined by eguations (6) to (8) #i5, = [MLL oO) M+L—+ML kK mon [ML ~@ ML+L—> Mi K)= iM) (Mba) 8) Mii +L—> My Ke= Mo Equation (6) can be written as [ML] = K; (Mj [L) = @) ‘Eguation (7) can be written as (Mba) = Ky (ML) UL) a, ‘Substituting the value of [ML] from equation (9) in (10), [Mba] = Ki: [LP iM] ‘Similarly, equation (8) can be written as [Mg] = Ki, KaK...-Ke[LI"(M] (12) Bjerrum introduced a function 7, which is defined as the average number of ligand molecules bound per mole of metal it may be expressed mathematically as : ge MLI+2 [MLo] + 3IMLa}+..# nlMLa} (13) (M) + [ML] + (ML2] + (ML) +... + [ML] ‘Substituting eqs. (9), (11) and (12) in (13) we get (Ky(MYL] + 2K KM] [L)?+ nk; Ko Ky .. + KMILY? (0M) + Ky(MIIL] 4K, KAMIILP + + Ky Ka Ks Kel] (L] ‘Cancelling “M" throughout, we get j= KIMIILI+ 2K; Ko + nk Ka Ka KL (4) 1+ KifL] + Ki Koll +... + Ki Kp Ka +... KelL] Equation (14) isthe so called Bjerum formation function. Ifthe conccetration of unbond ligand (A) can be calculated experimentally, i can be calculated form the equation : ili ld) M, where L, and M, denote the total concentration of ligand and metal respectively. ‘Solution of equation (14) for the known values of n and corresponding (L) values yields values of the formation constants, ie Kj, Kay K3.0Ke- Let us illustrate the Bjerrum method by calculating the formation constants for the complex between ‘CuSO, and $-sulphosalicylic acid (FisL). Procedure Titrate 100 ml of each solution £e., CuSO, and 5- sulphosalicylic acid with standard NaOH solution at 25°C , noting the pH values after addition of the titrant base NaOH . Plot the pH versus ml of base ‘curves and note tho point of inflexion ofthe curve corresponding to the mixed solution (Fig. 1262). Read off the horizontal distance between the curves. Thus find values of Fad plot the formation curve of ‘FW against —log (L*], the values of the latter having been found at various pH from the relation : fieYd mi of 0.1 NaOH Soin, —— teat — Fe.1242 Petana ano Tat} prenace Fo, 12.68. The fomaton cane (isd 2 (Cul ig 6 ee. on, (Ka Kin) ~ (Kar) ss Sta Hr woth second an i soration const o Hy wich ae 32310" ad ‘Tho yalues of K and Kz found from the formation curve (Fig. 12.63) at W=0.5 and W=15 are Ky=2210" and K2=6.3 x I 5. Polarographic Method : This method is based on the fact that the reduction potentials of metal ions are usually shifted tothe more negative values asa result of complex formation. Conse the reaction: ar Mia + ne + Hg “> Milg+ mL ss which may be imagined to occur in two steps :» 18) Min > M+ mL ™ ® ) M4 ne + Hg > Miig+ mL. where k, ky and kz correspond to respective formation constants of the above reaction ; M is the meal, the ligands, ML, isthe complex compound and w is the number of electrons involved in the reduction Lingane derived from the above reactions a relation connecting the potential at the dropping mercury cathode, E, the half wave poteral Eqs, the current i and th Limiting curent ig (the maximum of tho Polarographic wave)v bee og M™) equal to 2, Thus, the observed voltage is direcily related to the free motel ion concentations in the ells In practice successive portions of ligands tare added to the metal ion solution in one cell, and the corresponding voltages measured. From the known total concentration of the metal ion, ligand, and uncomplexed metal ion, the stability constant may be evaluated.