Determination

of the
Stability Constant
of a Metal Complex
 INTRODUCTION
Metal Complex
~ “Coordination compounds”
Coordinate bond

Central metal
Ligand
 INTRODUCTION
Equilbrium Constant
~ “Formation or Stability Constant”
~ Standard measure of the
effectiveness of the ligand in
coordinating with the metal ion
 INTRODUCTION
Equilbrium Constant

Ex. M + n L ⇌ M L n 𝑀𝐿𝑛
𝛽𝑛 =
𝑀 𝐿𝑛
Relationship:

𝑀𝐿𝑛 ⇆ 𝛽𝑛 [𝑀][𝐿]𝑛
 INTRODUCTION
Equilbrium Constant
[𝑀𝐿𝑛] = 𝐶𝑀 − [𝑀] [𝐿] = 𝐶𝐿 − 𝑛[𝑀𝐿𝑛]
𝑀𝐿𝑛
𝛽𝑛 = 𝑛
𝑀 𝐿
𝑀𝐿𝑛
log = 𝑛 log 𝐿 + log 𝛽𝑛
𝑀
 INTRODUCTION
Potentiometry
Determine:
✓ Composition of a complex
~ [free metal ion] and [free ligand ion]
✓ Stability constant
 INTRODUCTION
Irving-Williams Order of Stability
Order of Stability constant for the formation of
the complexes follows:
Mn < Fe < Co < Ni < Cu > Zn
Relative to:
✓ Nature of the coordinated ligands

✓ N u m b e r of ligands
 INTRODUCTION
Irving-Williams Order of Stability
Influenced by:
✓ Ionic radius ✓ Nature of ligand
✓ Ionic potential ✓ Electron-donating power
✓ Electronegativity of ligand
✓ Charge of the metal ✓ Entropy effect
✓ Hybridization of the ✓ Steric effect
metal
 METHODOLOGY

Step 3
Step 2
Step 1 ● Potentials of the M
a nd Cl electrodes
● The metal electrode
were measured
was placed in the cell
● A 200 m L of 1 x 10^-3 ● 5 m L increments of 5
together with a Cl
M MCl 2 ( M= Cu, C d or x 10^-2 M NaCl was
electrode a nd SCE.
Zn) was placed o n a added
● System was
cell
equilibrated
● The cell was
thermostated at the
working temperature
of 25˚C
 METHODOLOGY

Step 6
Step 5
The free chloride ion and
Step 4 The total metal
free metal ion
concentration were
ion concentration
The preceding procedure determined from the
a nd total ligand
was repeated until a total corresponding electrode
ion concentration
of about 100 m L of the potentials using the
were k n o w n by calculation
NaCl ha d been added. appropriate calibration
where the a m ount
curve
of dilution was factored in.
 RESULTS
y- intercept: Plot of: Where in:

β1 𝐴 𝑣𝑠 [𝐶𝑙−] 𝐴𝑀 𝐿 =
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
𝑓𝑟𝑒𝑒 [𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
𝐴=
[𝐴𝑀 𝐿 − 1൧
𝐶𝑙−

𝐴𝑀 𝐿 − 1൧
β2 − 𝛽1
𝐵 𝑣𝑠 [𝐶𝑙−] 𝐵=
𝐶𝑙−
𝐶𝑙−

β3 𝐶 𝑣𝑠 [𝐶𝑙−] 𝐵 − 𝛽2
𝐶=
[𝐶𝑙−]

β4 𝐶 − 𝛽3
𝐷 𝑣𝑠 [𝐶𝑙−] 𝐷=
[𝐶𝑙−]
 RESULTS : COPPER
Potentiometric Titration of 200 m L 1 x 10-3 M CuCl 2 with 5 x 10-2 M NaCl
Addition (mL) Cu2+ Pot. (MV) Cl Pot. (MV) Free [Cu2+] Free [Cl-] Total [Cu2+]
0 10 137.5 0.00096 0.001462 0.001
3 11.7 128.9 0.0008913 0.002879 0.0009804
6 13.6 122.4 0.0007852 0.003462 0.0009615
9 14.7 118.3 0.0007178 0.003892 0.0009434
12 15.7 115.3 0.0006683 0.004292 0.0009259
15 16.5 111.2 0.0006397 0.004462 0.0009091
18 17.7 107.1 0.0005957 0.004842 0.0008929
21 18.5 104.5 0.0005623 0.005395 0.0008772
30 22.1 99.8 0.0004365 0.007498 0.0008333
40 25.5 93.5 0.0003428 0.008318 0.0007895
50 28.8 90.8 0.0002754 0.009162 0.00075
60 30.5 87 0.0002455 0.01059 0.0007143
80 35.4 82 0.0001758 0.01228 0.0006522
100 41.8 79.2 0.0001122 0.01429 0.0006
120 46.2 77 0.00008318 0.01585 0.0005555
140 49.7 74.4 0.00006331 0.01721 0.0005172
 RESULTS : COPPER
Free [Cl-] AM(L) AM(L) - 1 A 𝑡𝑜𝑡𝑎𝑙 𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
0.001462 1.041667 0.041667 28.499772 Where: 𝐴𝑀 𝐿 =
𝑓𝑟𝑒𝑒 [𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
0.002879 1.099966 0.099966 34.72259163
0.003462
0.003892
1.224529
1.314294
0.224529
0.314294
64.85522313
80.75377059
[𝐴𝑀 𝐿 − 1൧
𝐴=
0.004292 1.385456 0.385456 89.80792957 𝐶𝑙−
0.004462 1.421135 0.421135 94.38254303
0.004842 1.498909 0.498909 103.0377626
0.005395 1.560021 0.560021 103.8037703
0.007498 1.909049 0.909049 121.2388978
0.008318 2.303092 1.303092 156.659315
0.009162 2.723312 1.723312 188.0933799
0.01059 2.909572 1.909572 180.3184421
0.01228 3.709898 2.709898 220.6757012
0.01429 5.347594 4.347594 304.2402787
0.01585 6.678288 5.678288 358.251612
0.01721 8.169326 7.169326 416.5790553

β1 = -20.55898
 RESULTS : COPPER
Free [Cl-] A – β1 B
0.001462 49.05897952 33556.07354
0.002879
0.003462
55.2814526
85.41426548
19201.61605
24671.94266
Where: 𝐴𝑀 𝐿 − 1൧
− 𝛽1
0.003892 101.3128336 26031.04665 𝐶𝑙−
0.004292 110.3669944 25714.58398 𝐵=
0.004462 114.9415434 25760.09489 𝐶𝑙−
0.004842 123.5967738 25525.97559
0.005395 124.3626867 23051.47111
0.007498 141.7978432 18911.42214
0.008318 177.2182726 21305.39464
0.009162 208.6524089 22773.67484
0.01059 200.8773931 18968.59236
0.01228 241.2347124 19644.52056
0.01429 324.7992874 22729.13138
0.01585 378.8105884 23899.72166
0.01721 437.1380614 25400.23599

β2 = 25,580.73347
Free [Cl-]
RESULTS : COPPER
B – β2 C
0.001462 7975.354079 5455098.549

Where:
0.002879 -6379.110311 -2215738.211
0.003462 -908.7848983 -262502.8591
0.003892 450.3184447 115703.6086 𝐵 − 𝛽2
0.004292 133.8552772 31187.15686 𝐶=
0.004462 179.3660065 40198.56712
[𝐶𝑙−]
0.004842 -54.75364959 -11308.06476
0.005395 -2529.258563 -468815.3035 β3 Determination
0.007498 -6669.308599 -889478.3408 6000000

0.008318 -4275.336369 -513986.0987 4000000 y = -8E+ 07x + 593 746

R² = 0.0615
2000000
0.009162 -2807.056395 -306380.3094

C
0
0.01059 -6612.139176 -624375.7484
-2000000
0.01228 -5936.211249 -483404.8248
-4000000
0.01429 -2851.600658 -199552.1804 0 0.005 0.01 0.015 0.02

0.01585 -1681.010517 -106057.4459 [Cl-]

0.01721 -180.4962884 -10487.87265

β3 = 593,745.5522
Free [Cl-]
RESULTS : COPPER
C – β3 D
0.001462 4.86E+06 3325138849
0.002879 -2809483.764 -975854033.9
0.003462 -856248.4114 -247327675.1 Where:
0.003892 -478041.9436 -122826809.8
𝐶 − 𝛽3
0.004292 -562558.3954 -131071387.5 𝐷=
0.004462 -553546.9851 -124058042.4 [𝐶𝑙−]
0.004842 -605053.617 -124959441.8
0.005395 -1062560.856 -196952892.6
0.007498 -1483223.893 -197815936.6
0.008318 -1107731.651 -133172836.1
0.009162 -900125.8616 -98245564.46
0.01059 -1218121.301 -115025618.6
0.01228 -1077150.377 -87715828.75
0.01429 -793297.7326 -55514187.03
0.01585 -699802.9981 -44151608.71
0.01721 -604233.4249 -35109437.82

β4 = 364, 667, 911.6

 RESULTS : CADMIUM
Potentiometric Titration of 200 m L 1 x 10-3 M CdCl 2 with 5 x 10-2 M NaCl
Addition (mL) Cd2+ Pot. (MV) Cl Pot. (MV) Free [Cd2+] Free [Cl-] Total [Cd2+]
0 681.6 143.0 9.226E-0 4 0.001778 1.0000E-03
2 682.8 137.8 8.395E-0 4 0.002213 9.9000E-04
4 684.5 134.2 7.345E-0 4 0.002512 9.8040E-04
6 685.0 129.8 7.063E-0 4 0.00302 9.7090E-04
8 685.5 126.5 6.792E-0 4 0.003428 9.6150E-04
10 686.0 122.2 6.546E-0 4 0.004027 9.5240E-04
12 686.8 120.6 6.145E-0 4 0.004315 9.4340E-04
14 687.4 118.5 5.864E-04 0.004667 9.3460E-04
20 688.4 114.0 5.420E-04 0.005559 9.0910E-04
30 689.3 108.8 5.058E-0 4 0.006761 8.6960E-04
40 690.3 104.3 4.667E-04 0.008035 8.3330E-04
50 692.1 101.7 4.064E-04 0.00912 8.0000E-0 4
60 693.7 98.2 3.589E-0 4 0.01012 7.6920E-04
70 695.1 96 3.218E-0 4 0.01122 7.4070E-0 4
80 696.5 93.5 2.897E-0 4 0.0123 7.1430E-04
100 698.2 89.5 2.530E-0 4 0.01429 6.67E-0 4
120 700.1 86.4 2.180E-0 4 0.01641 6.25E-0 4
140 701.6 82.2 1.939E-0 4 0.01884 5.88E-0 4
 RESULTS : CADMIUM
AM(L) AM(L) - 1
Free [Cl-] A
0.001778 1.084E+00 8.39E-02 47.18410849
𝑡𝑜𝑡𝑎𝑙 𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
Where:
0.002213 1.179E+00 1.79E-01 81.00920787
𝐴𝑀 𝐿 =
0.002512 1.335E+00 3.35E-01 133.2745097 𝑓𝑟𝑒𝑒 [𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
0.00302 1.375E+00 3.75E-01 124.0491208
0.003428 1.416E+00 4.16E-01 121.2473869
[𝐴𝑀 𝐿 − 1൧
0.004027 1.455E+00 4.55E-01 112.9710233
𝐴=
0.004315 1.535E+00 5.35E-01 124.0398368 𝐶𝑙 −
0.004667 1.594E+00 5.94E-01 127.2321905
0.005559 1.677E+00 6.77E-01 121.8395886
0.006761 1.719E+00 7.19E-01 106.3831716
0.008035 1.786E+00 7.86E-01 97.76170757
0.00912 1.969E+00 9.69E-01 106.1956071
0.01012 2.143E+00 1.14E+00 112.9659467
0.01122 2.302E+00 1.30E+00 116.0196267
0.0123 2.466E+00 1.47E+00 119.1588719
0.01429 2.635E+00 1.64E+00 114.4281222
0.01641 2.867E+00 1.87E+00 113.770413
0.01884 3.034E+00 2.03E+00 107.9364349

β1 = 105.96599
 RESULTS : CADMIUM
Free [Cl-] A – β1 B
0.001778 -58.78188389 -33060.6771

Where:
0.002213 -24.95678451 -11277.35405
0.002512 27.30851734 10871.22506 𝐴𝑀 𝐿 −
− 𝛽1
𝐶𝑙−1൧
0.00302 18.08312845 5987.790877
0.003428 15.28139455 4457.816381
0.004027 7.005030971 1739.51601
𝐵=
0.004315 18.07384444 4188.608212
𝐶𝑙−
0.004667 21.26619811 4556.716973
0.005559 15.87359623 2855.476925
0.006761 0.417179219 61.70377446
0.008035 -8.204284807 -1021.068427
0.00912 0.22961475 25.17705588
0.01012 6.999954294 691.6950884
0.01122 10.0536343 896.0458376
0.0123 13.19287957 1072.591835
0.01429 8.462129778 592.171433
0.01641 7.804420605 475.5893117
0.01884 1.97044256 104.5882463

β2 = -2607.361888
 RESULTS : CADMIUM
Free [Cl-] B – β2 C
0.001778 -3.05E+04 -1.71E+07

Where:
0.002213 -8669.992162 -3917755.157
0.002512 13478.58694 5365679.516
0.00302 8595.152764 2846077.074
0.003428 7065.178268 2061020.498
𝐵 − 𝛽2
𝐶=
0.004027 4346.877897 1079433.3 [𝐶𝑙 −]
0.004315 6795.9701 1574964.102
0.004667 7164.07886 1535050.109
0.005559 5462.838813 982701.7112
0.006761 2669.065662 394773.8
0.008035 1586.293461 197422.9572
0.00912 2632.538943 288655.5859
0.01012 3299.056976 325993.7723
0.01122 3503.407725 312246.6778
0.0123 3679.953722 299183.2295
0.01429 3199.533321 223900.1624
0.01641 3082.951199 187870.2742
0.01884 2711.950134 143946.3978

β3 = -1, 275,048.999
 RESULTS : CADMIUM
C – β3
Free [Cl-] D
0.001778
0.002213
-1.59E+07
-2642706.158
-8916085393
-1194173591
Where:
0.002512 6640728.515 2643602116
0.00302 4121126.073 1364611283
𝐶 − 𝛽3
𝐷=
0.003428 3336069.497 973182467.2 [𝐶𝑙 −]
0.004027 2354482.299 584674025
0.004315 2850013.101 660489710.5
0.004667 2810099.108 602121086
0.005559 2257750.71 406143319
0.006761 1669822.799 246978671.7
0.008035 1472471.956 183257244.1
0.00912 1563704.585 171458836.1
0.01012 1601042.771 158205807.4
0.01122 1587295.677 141470202.9
0.0123 1574232.229 127986360
0.01429 1498949.161 104894972.8
0.01641 1462919.273 89148036.15
0.01884 1418995.397 75318227.01

β4 = -624, 819, 578.6

 RESULTS : ZINC
Potentiometric Titration of 200 m L 1 x 10-3 M ZnCl 2 with 5 x 10-2 M NaCl
Addition (mL) Zn2+ Pot. (MV) Cl Pot. (MV) Free [Zn2+] Free [Cl-] Total [Zn2+]
0 1140 137 9.96E-0 4 0.0019 1.00E-03
2 1104.4 130.1 9.38E-0 4 0.00252 9.87E-0 4
4 1105.2 126.2 8.51E-0 4 0.00305 9.74E-0 4
6 1105.9 123.5 8.24E-0 4 0.00344 9.62E-0 4
8 1106.4 120.5 7.67E-0 4 0.0037 9.49E-04
10 1107 117.5 7.33E-0 4 0.00389 9.38E-0 4
15 1108.5 112.2 6.43E-0 4 0.00489 9.09E-04
20 1109.7 107.6 5.83E-0 4 0.00575 8.82E-0 4
30 1110.5 102.5 5.40E-04 0.00692 8.33E-0 4
40 1111.2 98.3 5.13E-0 4 0.00826 7.89E-0 4
50 1111.5 92 5.01E-0 4 0.0105 7.50E-0 4
60 1112 88.5 4.75E-0 4 0.012 7.14E-0 4
80 1113.1 85.5 4.42E-04 0.0133 6.52E-0 4
100 1113.6 83.5 4.22E-0 4 0.0145 6.00E-0 4
120 1114.6 82 3.86E-0 4 0.0156 5.56E-0 4
 RESULTS : ZINC
Free [Cl-] AM(L) AM(L) - 1 A
0.0019 1.00E+00 4.02E-03 𝑡𝑜𝑡𝑎𝑙 𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
Where:
2.11E+00
0.00252 1.05E+00 5.22E-02
𝐴𝑀 𝐿 =
2.07E+01 𝑓𝑟𝑒𝑒 [𝑚𝑒𝑡𝑎𝑙 𝑖𝑜𝑛
0.00305 1.14E+00 1.45E-01 4.74E+01
0.00344 1.17E+00 1.67E-01 4.87E+01 [𝐴𝑀 𝐿 − 1൧
0.0037 1.24E+00 2.37E-01 6.41E+01 𝐴=
0.00389 1.28E+00 2.80E-01
𝐶𝑙−
7.19E+01
0.00489 1.41E+00 4.14E-01 8.46E+01
0.00575 1.51E+00 5.13E-01 8.92E+01
0.00692 1.54E+00 5.43E-01 7.84E+01
0.00826 1.54E+00 5.38E-01 6.51E+01
0.0105 1.50E+00 4.97E-01 4.73E+01
0.012 1.50E+00 5.03E-01 4.19E+01
0.0133 1.48E+00 4.75E-01 3.57E+01
0.0145 1.42E+00 4.22E-01 2.91E+01
0.0156 1.44E+00 4.40E-01 2.82E+01

β1 = 57.82046415
 RESULTS : ZINC
Free [Cl-] A – β1 B
0.0019

Where:
-55.70674612 -29319.34006
0.00252 -37.09077924 -14718.56319 𝐴𝑀 𝐿 −
− 𝛽1
𝐶𝑙−1൧
0.00305 -10.43166409 -3420.217733
0.00344 -9.135659451 -2655.714957
𝐵=
0.0037 6.311464392 1705.801187 𝐶𝑙−
0.00389 14.07480023 3618.200574
0.00489 26.77786869 5476.046768
0.00575 31.3733609 5456.236678
0.00692 20.58887004 2975.270237
0.00826 7.314123735 885.487135
0.0105 -10.48656053 -998.7200501
0.012 -15.89063959 -1324.219965
0.0133 -22.09767301 -1661.479173
0.0145 -28.7307436 -1981.430593
0.0156 -29.58876493 -1896.715701

β2 = -6,473.429262
 RESULTS : ZINC
Free [Cl-] B – β2 C
0.0019 -22845.9108 -12024163.58
0.00252
0.00305
-8245.133928 -3271878.543 Where:
3.05E+03 1001052.96 𝐵 − 𝛽2
0.00344 3817.714305 1109800.67 𝐶 = [ −]
0.0037 8179.230449 2210602.824
𝐶𝑙
0.00389 10091.62984 2594249.315
0.00489 11949.47603 2443655.63
0.00575 11929.66594 2074724.511
0.00692 9448.699499 1365419.003
0.00826 7358.916397 890909.9754
0.0105 5474.709212 521400.8773
0.012 5149.209296 429100.7747
0.0133 4811.950088 361800.7585
0.0145 4491.998668 309793.0116
0.0156 4576.713561 293379.0744

β3 = -1, 338, 988.545

 RESULTS : ZINC
Free [Cl-]a C – β3 D
0.0019 -1.07E+07 -5623776334
0.00252 -1932889.998 -767019840.4 Where:
0.00305 2.34E+06 767226723.1
0.00344
𝐶 − 𝛽3
2448789.215 711857330
𝐷=
0.0037 3549591.369 959349018.7 [𝐶𝑙−]
0.00389 3933237.86 1011115131
0.00489 3782644.175 773546866
0.00575 3413713.056 593689227.2
0.00692 2704407.548 390810339.3
0.00826 2229898.521 269963501.3
0.0105 1860389.422 177179945
0.012 1768089.32 147340776.7
0.0133 1700789.304 127878895
0.0145 1648781.557 113709072.9
0.0156 1632367.62 104638950

β4 = -545, 473, 327.4

AVERAGE NUMBER OF LIGANDS
“Complex Formation Function”

σ 𝑁𝑖=1 𝑖𝛽 𝑖 [𝐿] Where:

ത
𝑛 i = 0 to 4
σ 𝑁𝑖=0 𝛽𝑖 [𝐿]𝑖 [Cl-] = 1 x 10-2 M
=
AVERAGE NUMBER OF LIGANDS
Copper

Cadmium

Zinc
 SUMMARY OF RESULTS
C u System C d System Z n System
β1 - 20.55898 + 105.96599 + 57.82046415
β2 + 25,580.73347 − 2607.361888 − 6,473.429262
β3 + 593,745.5522 − 1,275,048.999 − 1,338,988.545
β4 + 364,667,911.6 - 624,819,578.6 − 545,473,327.4
Average No.
of ligands
3 5 5
RESULTS : MOLE FRACTION
RESULTS : MOLE FRACTION
RESULTS : MOLE FRACTION
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Order of
C u System C d System Zn System
Stability

β1 – 20.55898 + 105.96599 + 57.82046415 Cd > Zn > Cu

β2 + 25, 580.73347 – 2, 607.361888 − 6, 473.429262 Cu > Cd > Zn

β3 + 593, 745.5522 – 1, 275, 048.999 − 1, 338, 988.545 Cu > Cd > Zn

β4 + 364, 667, 911.6 – 624, 819, 578.6 − 545, 473, 327.4 Cu > Zn > Cd
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Effect of Ionic Radius:

C a d m i u m & Nickel Stability depends o n ligand

Small ionic radius Less Stable complex
Large ionic radius More stable complex
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Effect of Ionization potential:

H i g h ionization Stable complex

potential
Lo w ionization Less stable complex
potential
Irving-Williams Order of Stability

Effect of Electronegativity:

Greater Greater stability

electronegativity
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Effect of Charge and Hybridization
of the metal :

Greater charge on Greater stability

metal
Greater hybridization Greater stability
of the metal
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Effect of nature of ligand and electron-
donating power of the ligand:
~ For C a d m i u m a n d Nickel
L has m o r e e- donating
power than H2O C d < Ni
L has less e- donating
power than H2O C d > Ni
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Effect of Entropy

Charged Increases as ionic

ligands radius decreases
Uncharged Negligible
ligands
Irving-Williams Order of Stability
Mn < Fe < Co < Ni < Cu > Zn
Effect of Steric hindrance
✓ Increase size of chelating rings
→less stability

*Less significant than ionization

potential and ionic radius*
THANK YOU!