Retrospective Theses and Dissertations

1961

Stability constants of some rare-earth-metal chelates Robert Harreld Karraker Iowa State University

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This dissertation has been 62—1353 microfilmed exactly as received KARRAKER, Robert Harreld, 1931STABILITY CONSTANTS OF SOME RARE-EARTHMETAL CHELATES. Iowa State University of Science and Technology Ph.D., 1961 Chemistry, inorganic University Microfilms, Inc., Ann Arbor, Michigan

STABILITY CONSTANTS OP SOME RABE-EARTH-METAL CHELATES by Robert Harreld Karraker

A Dissertation Submitted to the Graduate Faculty in Partial Fulfillment of The Requirements for the Degree of DOCTOR OF PHILOSOPHY Major Subjects

Inorganic Chemistry

Approved: Signature was redacted for privacy.

arge of Major Work Signature was redacted for privacy.

Head of Major Departmen Signature was redacted for privacy.

Dean/of Graduate College

Iowa State University Of Science and Technology Ames, Iowa

1961

ii TABLE OF CONTENTS Page INTRODUCTION

1

RARE-EARTH GLYCOLATE AND LACTATE STABILITY CONSTANTS

4

Review Methods of determining stability constants of metal complexes with organic acids Observed variations of some organic acid stability constants with metal and ligand Experimental Derivation of the experimental methods . Calculation of the margins of error

4 4 11 19 19 23

Materials and equipment

27

Procedure

29

Discussion RARE-EARTH DCTA STABILITY CONSTANTS

36 4?

Methods of Determining Strong Stability Constants

47

Experimental

50

Derivation of equations

50

Materials and equipment

53

Procedure

55

Discussion

59

SUMMARY

68

LITERATURE CITED

69

ACKNOWLEDGMENTS

74

iii Page APPENDIX! EXPERIMENTAL DATA FROM MEASUREMENT OF RARE-EARTH GLYCOLATE AND LACTATE STABILITY CONSTANTS

75

Lanthanum Glycolate

76

Cerium Glycolate

77

Praseodymium Glycolate

78

Neodymium Glycolate

79

Samarium Glycolate

80

Europium Glycolate

81

Gadolinium Glycolate

82

Terbium Glycolate

.

8

3

Dysprosium Glycolate

84

Holmium Glycolate

85

Erbium Glycolate

86

Thulium Glycolate

87

Ytterbium Glycolate

88

Lutetium Glycolate

89

Yttrium Glycolate

90

Lanthanum Lactate

91

Cerium Lactate

-

92

Praseodymium Lactate

93

Neodymium Lactate

94

Samarium Lactate

.95

Europium Lactate

96

Gadolinium Lactate

97

iv Page Terbium Lactate

98

Dysprosium Lactate

99

Holmium Lactate

100

Erbium Lactate

101

Thulium Lactate

102

Ytterbium Lactate

103

Lutetium Lactate

.104

Yttrium Lactate

105

1 INTRODUCTION

This dissertation is concerned with the measurement of the stability constants of several rare-earth complexes. Two separate types of complexes were studied in order to elucidate this phase of lanthanide chemistry.

The complexes'

of glycolic acid and lactic acid with the rare-earths were studied as examples of weak complexes and the complexes of rare-earths with 1,2-diaminocyclohexane-N,N,N1,N'-1etraacetic acid (DCTA), where only the 1:1 chelate is formed, were studied as examples of strong complexes. The separation of large amounts of pure rare-earths and yttrium by ion exchange was developed recently at Ames Laboratory (1,2,3) and has increased the availability of pure rare earths.

The process involves the use of ion-exchange

resins in conjunction with chelating agents. The basis of the separation is the exchange of metal ions between a cationexchange resin and an aqueous phase.

The ability of the

aqueous phase to compete with the resin for a rare-earth ion is due mainly to the complexing ability of the chelating agent used.

Chelate stability constants, then, permit an estimation

of the separation possible and the elution distance required (3).

Powell (4) has reviewed the application of chelating

agents to the ion-exchange separation of rare-earth mixtures. Aminopolyacetic acids have proven to be excellent chelat­ ing agents for use as eluants in the rare-earth separation

2 process (3,4) and stability constants have been determined previously for the rare-earth chelates of ethylenediamineN,N,N',N'-tetraacetic acid (EDTA) (5,6), N1(hydroxyethyl)ethylenediamine-N,N,N'-triaceti c acid (HEDTA) (5,7), 1,2-bis-C2-di(carboxymethyl)aminoethoxy]ethane (DE) (7,8), 2,2*-bis[di(carboxymethy1)amino3diethyl ether (ME) (7,8), and carboxymethyl-bis-32-di(carboxymethyl)-aminoethyllamine (DETEA) (9).

Stability constants for most of the rare-earth

chelates of DCTA have also been reported (6).

However, the

holmium-DOTA constant was not reported, and there, appeared to be a discrepancy in the relationship of the yttrium to the rest of the rare earths when the values were compared with the stability constant sequence obtained with EDTA. Glycolic and lactic acids have not been used for the separation of rare earths in macro-quantities; however, both have been used effectively for the separation of tracer quantities of the rare earths and actinides.

Freiling and

Bunney (10) have reported optimum conditions for rare-earth separations with ammonium lactate as the eluting agent. Cunninghame et al. (11) have also reported separations of the rare earths with lactate solutions.

Stewart (12) reported

separations of rare-earth tracers with an ammonia-buffered solution of glycolic acid.

Choppin, Harvey and Thompson (13)

compared the separation factors of glycol!c, lactic, and c [Gly-] x 103

n

n/[Gly'

1 2 4 6 8

4.03 4.91 5.30 5.19 4.88

0.403 O.836 1.781 2.873 4.187

0.250 0.414 0.687 0.912 1.075

620 495 386 317 257

10 12 14 16 20

4.69 4.47 4.34 4.13 3.91

5.528 7.030 8.502 10.266 13.641

1.235 1.354 1.483 1.537 1.688

223 193 174 150 124

24 28 32 38

3.75 3.58 3.47 3.33

17.136 21.002 24.812 30.767

1.810 1.839 1.884 1.892

105.6 87.6 75-9 61.5

10-3

x3

•ly-] x 103

XJ

X1

x2

X

0.3 1.0 2.0 3.0 4.0

1.247 1.826 2.759 3.872 5.174

823 826 880 957 1044

143 46 50 59 66

6.0 8.0 10.0 12.0 15.0

8.353 12.35 17.25 23.06 33.58

1266 1419 1625 I838 2172

74 80 85 88 93

2511 2976 3477 3923 4309

96 100 104 105 104

18.0 22.0 26.0 30.0 34.0

46.19 66.47 91.39 118.7 147.5

1.3 1.3 1.4 1.3 1.3 1.2

80 Samarium Glycolate

c A X io3 A

[H+] x 104

[Gly-] x lo3

n

n/[Gly"

1 2 4 6 8

4.13 5.32 5.75 5.57 5.27

0.387 0.751 1.620 2.658 3.857

0.257 0.445 0.739 0.975 1.168

664 593 453 367 303

10 12 14 16 20

4.95 4.76 4.54 4.37 4.09

5.223 6.585 8.116 9.687 13.029

1.318 1.473 1.585 1.688 1.845

252 224 195 174 141.6

24 28 32 38

3.85 3.66 3.55 3.41

16.684 20.537 24.246 30.039

1.925 1.957 2.027 2.076

115.4 95.3 83.60 69.I

[Gly-] x 103 0.3 1.0 2.0 3.0 4.0

Xj

1.252 1.905 3.040 4.440 6.133

X1

X2 X 10

840 905 1020 1147 1283

85 100 109 116

6.0 8.0 10.0 12.0 15.0

10.42 16.05 23.18 32.00 48.49

1570 1881 2218 2583 3166

125 133 140 147 156

18.0 22.0 26.0 30.0 34.0

68.53 101.1 141.5 190.5 247.6

3752 4550 5404 6317 7253

163 170 176 I83 189

Xo x 10- 6

tt

3.7 3.7

3.5

81 Europium Glycolate

c A x io3

[H+] x 104

[Gly-] x 103

n

n/[Gly'

l 2 4 6 8

4.23 5-32 5.81 5.66 5.36

0.371 0.751 1.601 2.611 3.788

0.263 0.445 0.745 0.989 1.187

709 593 . 465 379 313

10 12 14 16 20

5.07 4.86 4.57 4.37 4.13

5.093 6.444 8.061 9.687 12.899

1.354 1.511 1.599 1.688 1.879

266 234 198 174 146

24 28 32 38

3-87 3.72 3.56 3.39

16.596 20.201 24.177 30.219

1.948 2.043 2.045 2.030

117 101.1 84.6 67.2

[Gly-] x 103 0.3 1.0 2.0 3.0 4.0

xJ

1.266 1.965 3.169 4.661 6.470

X1

X2 x 10

887 965 1085 1220 1368

90 105 113 120 127

6.0 8.0 10.0 12.0 15.0

11.10 17.15 24.73 34.03 51.79

1683 2019 2373 2753 3386

137 145 151 158 168

18.0 22.0 26.0 30.0 34.0

74.61 112.7 158.8 212.9 277.1

4089 5077 6069 7063 8121

179 192 200 207 214

Xj x 10"6

3.3 3.3 3-3

3:S 3.2

82 Gadolinium Glycolate

CA x 103

[H+] x 104

[Gly-] x 103

n

n/[Gly'

1 2 4 6 8

3.81 4.76 5.24 5.15 4.84

0.442 0.871 1.804 2.897 4.224

0.235 0.401 0.680 0.905 1.065

532 460 377 312 252

10 12 14 16 20

4.69 4.47 4.26 4.13 3.91

5.528 7.030 8.667 10.266 13.641

1.235 1.354 1.440 1.537 1.688

223 193 166 150 124

24 28 32 38

3.72 3.55 3.44 3.33

17.276 21.182 25.030 30.767

1.774 1.743 1.829 1.892

102.7 84.6 73.1 61.5

[Gly-] x 103

xJ

X1

X2 x 10-3

x 10- 6

0.3 1.0 2.0 3.° 4.0

1.192 1.686 2.514 3.507 4.673

640 686 757 836 918

69 72 75

6.0 8.0 10.0 12.0 15.0

7.524 11.07 15.37 20.77 30.28

1087 1259 1437 1648 1952

78 80 82 86 89

1.00 1.00 1.00 1.17 1.13

2268 2690 3102 3513 3909

92 94 95 96 97

l.ii 1.00 0.88

18.0 22.0 26.0 • 30.0 34.0

41.82 60.17 81.63 106.4 133.4

83 Terbium Glycolate

CA X io3

[H+] x 104

[Gly"] x 103

n

n/[Gly'

l 2 4 6 8

3-87 4.84 5.24 5.27 4.95

0.431 0.852 1.804 2.825 4.124

0.239 0.408 0.680 0.926 1.093

555 479 377 328 265

10 12 14 16 20

4.72 4.51 4.42 4.23 4.00

5.491 6.9&5 8.343 10.016 13.328

1.245 1.372 1.525 1.602 1.768

227 197 183 160 133

24 28 32 38

3.78 3.61 3.50 3.39

16.998 20.825 24.597 30.218

1.845 1.884 1.938 2.030

108.5 90.5 78.8 67.2

[Gly] x lo3

Xj

0.3 1.0 2.0 3.0 4.0

1.199 1.716 2.572 3.605 4.815

6.0 8.0 10.0 12.0 15.0

7.777 11.50 16.15 21.84 32.42

18.0 22.0 26.0 30.0 34.0

45.32 66.01 91.17 121.8 157.8

X1

x2 X 10-3

X. x 10-6

663 716 786 868 954

56 63 69 74

1130 1313 1515 1737 2095

78 82 86 90 96

1.00

100 104 108 112 116

1.05 1.05 1.04 I.03 1.03

2462 2955 3468 4027 4612

84 Dysprosium Glycolate

CA x 103

[H+] x 104

[Gly-] x 103

n

4.14 5.15 5.62 5.50 5.24

0.385 0.784 1.664 2.695 3.881

0.257 0.433 0.725 0.964 1.161

668 552 436 358 299

10 12 14 16 20

4.99 4.76 4.52 4.38 4.09

5.179 6.585 8.153 9.664 13.029

1.330 1.473 1.575 1.694 1.845

257 224 193 175 142

24 28 32 38

3.91 3.71 3.61 3.47

16.424 20.256 23.839 29.515

1.992 2.029 2.131 2.208

121 100.2 89.4 74.8

1 2 4 6 8

[Gly"] x 103 0.3 1.0 2.0 3.0 4.0

Xj

1.254 1.890 2.971 4.305 5.919

X1

.

X2 x 10-3

847 890 986 1102 1230

73.0 87.3 97.5

6.0 8.0 10.0 12.0 15.0

10.04 15.42 22.21 30.61 46.49

1507 1803 2121 2468 3032

111.2 120.4 128.1 135.7 146.2

18.0 22.0 26.0 30.0 34.0

66.70 101.0 144.5 197.3 259.3

3650 4545 5519 6543 7597

156.1 168.4 180.0 190.1 198.7

n/[Gly'

Xc x 1CT6

3.4 3-5 3-5 3.5 3.5 3.4

85 Holmium Glycolate

CA x 103

[H+] x 104

[Gly-] x 103

n

n/[Gly'

1 2 4 6 8

4.34 5136 5.81 5.57 5.36

0.355 0.743 1.601 2.658 3.788

0.270 0.448 0.745 0.975 1.187

761 603 465 367 313

10 12 14 16 20

5.04 4.80 4.57 4.40 4.07

5.125 6.528 8.061 9.619 13.094

1.345 1.488 1.599 1.705 1.828

262 228 198 177 140

24 28 32 38

3.91 3.75 3.66 3.48

16.424 20.037 23.509 29.429

1.992 2.085 2.214 2.230

121 104.1 94.2 75.8

10-3

Xj x 10

[Gly-] x 103 0.3 1.0 2.0 3.0 4.0

Xj

1.307 2.076 3.344 4.890 6.761

X1

1023 1076 1172 1297 1440

x2

X

96 106 115

6.0 8.0 lOoO 12.0 15.0

11.56 17.91 25.61 35.16 53.03

1760 2114 2461 2847 3469

130 142 148 l66

3-3 4.0 3.8 3.8 3.7

18.0 22.0 26.0 30.0 34.0

75.92 115.3 166.3 231.0 309.2

4162 5195 6358 7667 9065

177 192 207 223 238

3.7 3.7 3-7 3.8 3.8

86 Erbium Glycolate

CA x 103

[H+] x 104

[Gly-] x 103

îï

n/[Gly~]

1 2 4 6 8

4.4? 5.73 6.18 6.04 5.71

0.337 0.677 1.489 2.430 3.539

0.278 0.474 0.782 1.044 1.258

825 700 525 430 355

10 12 14 16 20

5.36 5.01 4.80 4.57 4.26

4.803 6.243 7.661 9.251 12.498

1.433 1.565 1.705 1.802 1.982

298 251 223 195 159

24 28 32 38

4.00 3.91 3.75 3.61

16.048 19.206 22.939 28.360

2.088 2.296

130 120 102.7 88.1

X2 x 10-3

Xj x 10

[Gly-] x 103 0.3 1.0 2.0 3.0 4.0 6.0 8.0 10.0 12.0 15.0 18.0 22.0 26.0 3O.O 34.0

Xj

1.313 2.136 3.636 5.558 7.966 14.25 22.72 33.73 47.65 74.79 110.7 173.3 257.9 366.5 501.9

X1

.

ïttî

1043 1136 13181519 1742

110 126 154 170 183

2208 2715 3273 3888 4919

200 213 226 240 261

6094 7832 9881 12183 14732

282 310 341 372 404

7.3 7.1 7.1 7.1 7.1 7.0 7.2 7.2

87 Thulium Glycolate

CA x 103

[H+] x 104

[Gly"] x 103

EL

11/[Gly'

1 2 4 6 8

4.69 5.98 6.64 6.38 5-98

0.308 0.638 1.367 2.286 3.367

0.290 0.490 0.824 1.088 1.308

942 768 603 476 388

10 12 14 16 20

5.57 5.24 4.95 4.72 4.37

4.611 5.957 7.421 8.948 12.177

1.487 1.642 1.769 1.881 2.065

322 276 238 210 170

24 28 32 38

4.09 3.91 3.78 3.61

15.689 19.206 22.754 28.360

2.180 2.296 2.406 2.498

139 120 105.7 88.1

X2 x 10"3

X3 x 10

[Gly"] x 103 0.3 1.0 2.0 3.0 4.0

Xj

1.363 2.338 4.167 6.555 9.551

6.0 8.0 10.0 12.0 15.0

17.61 28.83 43.79 62.72 100.2

18.0 22.0 26.0 30.0 34.0

149.2 235.2 350.9 500.4 692.5

%1 1210 1338 1584 1852 2138

250 203 225 239 251

9.5

2768 3469 4279

272 314 314 334 365

9.8 10.1 10.1 10.1 10.1

8233 10645 13458 16647 20338

394 432 474 517 565

10.1 10.0 10.0 10.1 10.4

m

88 Ytterbium Glycolate

cA x

IQ3

l

2 4 6 8

10 12 14 16 20

£H+]

x

IO4

4.93 6.30 6.79

6.51 6.11

5.60 5.27

4.99 4.74 4.40

24 "28

4.11

32 38

3.61

[Gly-] x lO 3 0.3 1.0 2.0 3.0 4.0

3,92 3.76

Xj

1.423 2.589 4.696 7.423 10.89

6.0 8.0 10.0 12.0 I5.O

20.30 33.46 51.02 73.72 118.3

18.0 22.0 26.0 30.0 34.0

177.5 281.6 420.3 599.5 829.5

[Gly - ] x

0.280 0.591 1.330 2.277 3.334 4.585 5.922 7.359 8.909

12.092

15.611 19.157 22.877 28.360

X1

10 3

n 0.303

0.510 0.837

1.094 1.319

1.494 1.651 1.785

11/[Gly'

1082 863 629

480

396

326 279 243

1.891 2.087

212 178

2.200

141 121 103.8

2.309 2.375 2.500

Xg x 10-3

88.2

y- y i n"6

1410 1589 1848 2141 2473

200 239 249 264 281

3217 4058 5002 6060 7820

311 339 365 393 431

12.7 13.0 13.0 13.2 13.1

470 518. 568 620 677

13.1 12.9 12.8

9806 12755 16127 19950 24368

12.8 13.0

89 Lutetium Glycolate

n/[Gly'

[Gly-] x 103

n

4.97 6.59 7.15 6.85 6.32

0.275 0.553 1.250 2.110 3.171

0.306 0.527 0.866 1.144 1.365

1113 953 693 542 430

10 12 14 16 20

5.87 5.47 5.13 4.88 4.51

4.362 5.695 7.151 8.646 11.790

1.556 I.713 1.841 1.961 2.165

357 301 257 227 184

24 28 32 38

4.20 3.98 3-81 3.66

15.271 18.864 22.573 27.968

2.287 2.384 2.452 2.600

150 126 108.6 93.0

CA x 103 1 2 4 6 8 '

-] x 103 0.3 1.0 2.0 3.0 4.0

[H+] x 104

Xj

1.433 2.718 5.177 8.483 12.71

X1

X2 x lO"3

X. x :

1443 1718 2089 2494 2928

318 345 365 382

18

6.0 8.0 10.0 12.0 15.0

24.46 41.26 64.15 94.41 155.2

3910 5033 6315 7784 10280

418 454 492 532 592

20 19 19 19 19

18.0 22.0 26.0

236.5 382.4 581.1

13083 17336 22312

649 724 804

19 19 19

\-6

90

Yttrium Glycolate

cA x io3

[H+] x 104

[Gly-] x 103

n

n/[Gly"

l 2 4 6 8

3.72 &.65 5.12 4.99 4.80

0.452 0.885 1.826 2.954 4.199

0.230 0.395 0.672 0.886 1.070

509 446 368 300 255

10 12 14 16 20

4.57 4.43 4.26 4.09 3.87

5.596 6.992 8.540 10.216 13.582

1.215 1.363 1.472 1.548 1.701

217 195 172 152 125

24 28 32 38

3.70 3.52 3.41 3.29

17.116 21.050 24.882 30.686

1.814 1.826 1.865 1.911

106.0 86.7 75.0 62.3

[Gly-] x 103

xJ

X1

-3 %2 % :10

0.3 1.0 2.0 3.0 4.0

1.184 1.664 2.467 3.420 4.511

613 664 734 807 878

54 62 66 67

6.0 8.0 10.0 12.0 15.0

7.168 10.54 14.67 19.61 28.56

1028 1193 1367 1551 1837

70 73 76 78 82

2132 2532 2944 3367 3791

85 87 90 92 94

18.0 22.0 26.0 30.0 34.0

39.38 56.71 77.55 102.0 129.9

X3 x 10-5

4.7 5.6 5-5 5-8

1:1

91

1

2 4 6 8

H O -Pr

X

i )

C A x 10 3

i—i

Lanthanum Lactate

2.96 3.61

[Lac - ] x 10 3

n

0.561 1.071 2.216 3.442 4.799

0.184 0.323 0.542 0.736 0.894

302 245 214 186

6.283 7.809

1.020 1.136

145

14.377

1.414

136 125 98.4

n/[Lac'

328

20

3.85 3.85 3.75 3.62 3.52 3.47 3.39 3.23

24

3.13

17.860

1.613

90.3

32 38

2.96 2.87

25.278 31.011

1.755

69.4

1.819

10 12 14 16

28

[Lac™] x 103

0.3 2.0 3.0

1.0

9.286 10.903

Xj

1.122 1.415

1.869

2.371

4.0

2.929

6.0 8.0 10.0 12.0

4.217 5.795 7.619 9.768

15.0

13.60

18.0 22.0 26.0 30.0 34.0

18.15

25.39 33.89 43.83

55.04

xl

-

407 415

1.265 1.359

Xg x 10-3

435 457

15.0 17.5 14.0

536

22.7

482 599

662

731

24.9 26.2 27.6

29.3

953

30.7 32.2 33.3 35.4 35.0

1589

58.7

Xo x 10-5

20.5

840

1109 1265 1461

162

3.6 4.2 4.7 4.9 4.8 4.6 4.4 4.5

92 Cerium Lactate

CA X io3

[H+] x 104

[Lac"] x 103

n

0.433

0.208

236 212

1 2 4 6 8

4.13 4.61 4.69 4.54

4.25

4.301

0.850 1.015

10 12 14 16

4.11 3.91

5.604

1.190

24

3.26 3.16 3.06 2.95

20

28 32 38

[Lac"] x 103

3.78 3.61 3.42

xj

0.3 1.0

1.175

2.0 3.0 4.0

2.302 3.124

6.0 8.0 10.0 12.0 15.0

18.0 22.0 26.0 30.0

34.0

0.875 1.862 2.971

185

10.335 13.682

167 145 122

17.261

1.769 1.885

102.5 90.6

1.940 2.008

66.3

20.802 24.575

30.300

X1

583 651

4.074

708 769

6.375 9.276

896

24.46

33.64 48.67 67.22

89.54

115.6

336 286

1.436 1.503 I.665

605

16.93

480 415

1.312

7.110 8.611

1.605

12.78

0.363 0.625

n/[Lac"

1035 1178 1328 1564 1813 2167

2547 2951 3371

X2 x 10-^

78.9

Xj x 10-5

43.3 35.0 40.5

46.0

50.0 54.3 58.1 60.8 63.2 66.3 69.1 72.6 76.0 79.4

82.4

8.5 8.9 8.9 8.8 8.8 8.6

8.9

93

[H+] x 104

3.64

1 2 4 6 8

4.43 4.76 4.57

10 12 14 16 20

4.23 4.00 3.78 3.65 3.47

24 28 32

3.23 3.16

33

[Lac-] x 10 3 0.3 1.0

2.0 3.0 4.0 6.0 8.0

10.0

12.0

15.0 18.0

22.0 26.0 30.0 34.0

4.37

3.01

2.91

Xj 1.217 1.772 2.695 3.786 5.062

8.282 12.44 17.47 23.35 33.93 46.98 68.94

95.94

127.6 173.0

X

CA x 103

1—1 £ 0 1 11

Praseodymium Lactate

0.407 0.819

1.725 2.826 4.032 5.275 6.757 8.397 9.981 13.196

17.080 20.413 24.538 30.193

yvl

723 772 848 929

1016

'.

103

n

1.101

587 496 . 399 321 273

1.287

244

0.239 0.406 0.688

0.908. 1.411

178

1.811 1.976 1.941

106 96.8 78.1

2.025

X2 x 10~3

67.1

Xc x 10

67.0 71.5 74.7 77.8 84.8

2195

96.5 99.3

2554

102.7

3652

135

60.0

90.6 94.2

4220 4765

209 160

1.495 ' 1.596 1.788

1214 1430 1647 1863

3088

n/[Lac

108.3 113.3 117.2 119.4

1.3 1.4 1.4 1.3 1.3 1.3 1.3 1.2

94

Neodymiura L a c t a t e

CA x 103

[H+] x 104

[Lac™] x 103

n

n/[Lac

1 2 4 6 8

3.72 4.65 4.95 4.74 4.51

0.393 0.769 1.650 2.716 3.900

0.245 0.424 0.711 0.940 1.138

623 551 431 346 '292

10 12 14 16 20

4.26 4.03 3.85 3.72 3.50

5.236 6.705 8.240 9.789 13.081

1.298 1.425 1.536 1.646 1.817

248 213 186 168 139

24 28 32 38

3.28 3.16 3.01 2.96

16.816 20.413 24.538 29.679

1.878 1.976 1.941 2.154

112 96.8 79.1 72.6

x 10™3

X. x 10

~] x 103

h

X1

0.3 1.0 2.0 3.0 4.0

1.227 1.833 2.873 4.124 5.611

757 833 937 1041 1153

6.0 8.0 10.0 12.0 15.0

9.305 14.10 20.15 27.51 41.28

1384 1638 1915 2209 2685

" 107 112 . 118 122 130

2.3 2.4 2.5 2.4 2.5

3191 3908 4669 5477 6297

136 144 151 158 163

2.4 2.3 2.2

18.0 22.0 26.0 30.0 34.0

58.43 86.98 122.4 165.3 215.1

93.0 98.5 100 103

2.8 2.3 2.5

95

Samarium Lactate

CA x 103

[H+] x 104

[Lac""] x 103

n

n/[Lac

1 2 4 6 8

3.78 4.80 5.19 4.95 4.65

0.383 0.738 1.563 2.591 3.776

0.249 O.436 0.739 0.976 1.172

650 591 473 377 310

10 12 14 16 20

4.47 4.16 3.87 3.75 3.50

4.980 6.488 8.196 9.708 13.081

1.367 1.482 1.548 1.667 1.817

274 228 189 172 139

24 28 32 38

3.28 3.13 3.01 2.89

16.816 20.610 24.538 30.404

1.878 1.926 1.941 1.971

112 93.4 79.1 64.8

;-J X 103 0.3 1.0 2.0 3.0 4.0

Xj

1.230 1.376 3.035 4.449 6.145

%1

X2 x 10

\-6

767 876 1018 1150 1286

129 130 132

3.0 2.3 2.3

6.0 8.0 10.0 12.0 15.0

10.49 16.08 23.OI 31.51 47.50

1582 1885 2201 2543 3100

137 141 144 149 156

2.3 2.3 2.1

18.0 22.0 26.0 30.0 34.0

"67.41 99.15 136.3 178.9 228.3

3689 4461 5204 5930 6685

163 168 171 172 174

2.2

2.2 2.2

96 Europium Lactate

CA x 103

[H+] x 104

[Lac"] x

3.94 4.99

0.358 0.701

5.24 5.15 4.?6

1.546 2.482

10 12 14 16 20

4.4? 4.23 4.00

4.980

24 28 32 38

1 2 4

6 8

[Lac-] x 10^ 0.3 1.0 2.0 3.0 4.0

5

n/[Lac

O.259 0.450 0.746

642

723 483

1.008 1.198

406

325

1.367 1.512

274

1.620 1.707

204

3.81 3.55

6.377 7.922 9.552

12.894

1.865

145

3.33 3.18

16.560 20.283 24.293

1.943 2.009 2.003 2.154

117

10-3

X. x 10'

3.04 2.96

Xj

1.275 2.026

3.329 6.970

4.974

6.0 8.0 10.0 12.0 15-0

12.10

18.0 22.0 26.0 30.0

81.10 121.8 172.3

34.0

3.683

LO?

18.95 27.56 37.93 57.07

232.3 300.5

29.679

X1

917 1026 1165

1325 1493 1850

2244

2656

3098 3738

4450 5491 6588 . 7710

8809

x2 x

237

179 99.0

82.5

72.6

138 145 151 160 1.69 177 184 190 198

209

219

227 233

2.4 2.7 2.8

2.7 2.7 2.7

2.7

2.6

97

Gadolinium Lactate

CA x 103

[H+j x 104

[Lac™] x 103

0.372

0.253

680

0.761 1.605

0.427

561 452 366 296

1 2 4 6 8

3.85 4.69 5-07 4.88 4.54

10 12 14 16

4.30

2.632 3.873 5.186

3.64

6.603 8.240 10.009

3.57 3.26 3.13 2.96 2.89

16.920 20.610 24.956 30.404

20

24

28

32 38

[Lac"] x ID3 0.3 1.0 2.0 3.0 4.0

4.09 3.85

Xj

1.246 I.885

3.005 4.374 5.996

6.0 8.0 10.0 12.0 15.0

10.03 15.26 21.62 29.34

18.0

60.57 87.85 120.7

22.0 26.0 30.0 34.0

43.48

159.3 203.5

n/[Lac'

n

13.196

X1

0.726

0.964 1.145

1.536 1.589 1.788

253 220 186 159 135

1.852

109

1.311 1.452

1.926

1.835 1.971

x2 x 10-3

•

93.4 73.5 64.8

Xo x 10

820 885 1003 1125

1249

1505 1783

2062 2362 2832

3309 4604 5277 5956 3948

112 115 117

1.7

121 124 128

1.8 1.8 1.8

132 137 141 144 147 150

152

1.8

1.8 1.8

1.7

98 Terbium Lactate

CA x 105

[H+] x 10^

[Lac-] x 10^

n

n/CLac'

1 2 4 6 8

3.78 4.95 5.41 5.12 4.80

0.383 0.708 1.490 2.497 3.650

0.249 0,44? 0.763 1.004 1.208

650 631 512 402 331

10 12 14 16 20

4.57 4.23 4.00 3.81 3.52

4.865 6.377 7.922 9.552 13.006

1.398 1.512 1.620 1.707 1.837

287 237 204 179 l4l

24 28 32 38

3.28 3.16 3.03 2.91

16.816 20.413 24.374 30.193

1.878 1.976 . 1.982 2.025

112 96.8 81.3 67.0

[Lac"] x lo3 0.3 1.0 2.0 3.0 4.0

xj

1.250 1.941 3.233 4.839 6.798

X1

X2 x 10

833 941 1117 1280 1450

164 163 165

6.0 8.0 10.0 12.0 15.0

11.91 18.62 27.18 37.61 56.76

1818 2203 2618 3051 3717

171 177 183 188 195

18.0 22.0 26.0 30.0 34.0

80.70 120.1 167.8 224.3 287.6

4428 5414 6415 7443 8429

202 210 216 222 225

Xj x 10-6

2.1 2.3 2.3 2.3 2.3 2.3

99 Dysprosium Lactate

CA x 103

[H+] x 104

[Lac-] x 10^

n

n/[Lac'

1 2 4 6 8

4.23 5.41 5.71 5.57 5.07

0.318 0.628 1.399 2.277 3.444

0.276 0.478 0.793 1.070 1.266

868 761 567 470 368

10 12 14 16 20

4.72 4.37 4.09 3-91 3.61

4.703 6.165 7.743 9.302 12.676

1.442 1.568 1.667 1.772 1.921

307 254 215 190 152

24 28 32 38

3.41 3.21 3.10 2.94

16.166 20.091 23.819 29.883

2.044 2.058 2.123 2.103

126 102.4 89.4 70.4

X% x 10-3

x 10'

[Lac"] x 103 0.3 1.0 2.0 3.0 4.0 6.0 8.0 10.0 12.0 15.0 18.0 22.0 26.0 3O.O 34.0

XJ

1.326 2.266 3.970 6.204 8.976 16.22 25.83 38.10 53.58 82.78 119.7 181.2 257.5 347.6 449.8

X1

1087 1266 1485 1735 1994

233 238 244

4.0 4.3 4.7

2537 3104 3710 4882 5519

253 261 269 280 300

4.7 4.5 4.4 4.6 5.0

6594 8191 9865 11553 13200

310 326 340 3% 358

4.7 4.6

100

Holmiura Lactate

CA x 103 1 2 4 6 8 10 12 14 16

20

24

28

32 38

[Lac-] x 103 0.3 1.0 2.0

3.0

4.0 6.0

8.0

10.0 12.0

15.0 18.0 22.0 26.0 30.0 34.0

[H+] x 104 4.26

5.50 6.04 5.85 ,5.27 4.84 4.51

4.26

4.00

3.70 3.44

3.23 3.13 2.96

Xj

1.329 2.295

[Lac"] x 103

n

0.314

0.278 0.484 0.824 1.107 1.306

885 788 629 513 395

1.476 1.621

322 272 236

0.614 1.310 2.157

3.304 4.581 5.967 7.424 9.087 12.362 16.023 19.965 23.588

29.679

%1 1097

1.751 1.828 2.002

162

2.080 2.090

130 104.7

2.154

92.5 72.6

2.181

Xg x 10

1295 1596 1898 2203

245 273 283 288

18.16

2860

29.62

3578 4351 5188

302 316 330 345 367 386

4.192 6.694

9.812

44.51

63.26 99.25

144.8

220.6

314=8

429.0 562.5

6550

7989 9982 12069 14267 16515

n/[Lac'

406 424 441 455

201

Xo x 10 - 6

2:§

& 6.8 6.9

7.0 6.4 6.5

101

Erbium Lactate

X 10 3

[H+] x 104

1 2 4 6 8

4.61

10 12 14 16

5.19 4.84 4.47 4.23

24 28 32 38

3.93 3.58 3.33 3.21 3.05

5-98 6.43 6.23 5.62

20

[Lac-] x 103 0.3 1.0 2.0

3.0

4.0 6.0 8.0 10.0 12.0

15.0 18.0

22.0 26.0 30.0

34.0

•

XJ

1.467 2.784

5.353 13.47 8.883

26.37 44.76 70.02 103.7 170.7 • 258.O

' 407.9 6o4.5

852.2 1157

[Lac"] x 103

n

0.272 0.546 1.216 2.011 3.084

0.297 0.513

4.256

5.544 7.065 8.580 11.625

15.387 19.359 22.994 28.797

X1

0.857

• 1092 940 705

1.370

444

1.566 1.735

368 313 261 229 189

1.153 .

1.846

1.961

2.192

2.243 2.244

2.332 2.377

X2 x 10 ™3

1557 1784 2177 2628

323

3118

415

4228

461 501 544

5470 6902 8558 11313 14278 18495 23250

28373 . 34000

n/[Lac'

573

146 116 101.4

82.5

X. x 10™6

324 359 389

592 657 712 .

774 838

897 957

14.3 15-8

16.2 16.1 16.1

102

Thulium Lactate

CA x 103

[K+] x 104

[Lac"] x 103

n

0.307 0.530

1218 1041

n/[Lac"

1 2

4.80 6.28

0.252 0.509

4

6.96

1.106

1.860 2.853

1.202 1.438

0.898

812

10

5.50

6 8

6.68 6.04

646 504

12 14 16 20

5.07 4.72 4.37 3.91

4.003

5.282 6.678 8.298 11.685

1.637

409

24 28

3.62 3.39

2.287 2.332

150 123

32 38

3.23 3.03

15.215 19.012 22.851

2.368

104

[Lac-] x

0.3 1.0

2.0 3.0 4.0

6.0 8.0 10.0 12.0 15.0 18.0

22.0 26.0 30.0 34.0

10 3

XJ

1.489 2.959 6.075 10.51 16.85 33.65 59.10 93.94 139.4 229.2 347.4 554.1 820.8 1153 1553

1.806 1.949 2.035 2.177

2.329

28.988

X1

1630 1959 2538 3170 3963 5442 7263 9294 11533 15213 19244 25141 31531

38400 45647

%2 x

10-3

342 292 245 186

80.3

Xj x 10"6

409 494 540 603 649 714 774 832

911

983 1072 1153 1228 1297

25.5 26.4 26.8 26.7 26.3

103

Ytterbium Lactate

CA x 103

[H+] x 104

5.07

1 2 4 6 8

6.64

10 12 14 16

[Lac-] x 103

n

xi/LLi

0.227 0.469 1.033

0.320

1410 1171 896 721

0.549 0.926 1.246 1.479

7.36 7.13 6.32

1.728

5.73 5.24 K.84

3.833 5.103 6.507 8.182

I.685

4.43

2.716

1.855 1.994 2.065

545 440 364 306

252

20

4.00

11.417

2.256

197

24

3.70 3.41 3.28 3.11

14.881 18.899 22.499 28.236

2.372 2.361

159 125

28

32 38

:"] X

0.3 1.0 2.0 3.0 4.0 6.0 8.0 10.0 12.0 15.0

18.0 22.0 26.0 30.0

10 3

XJ

1.559 3.301 7.129 12.74 20.83 42.68 75.92 121.4 181. 5 305.4 472.4 763.4 1147 1641

X1

I863

2301 3065 3913 4958

6847 9365 12040 15042 20290 26189 34655 44077 54667

2.457 2.519

%2 x IO-3

109

89

x

543 601 683

738 815

875 958 1034 1112

1239 1361

1498

1630 1766

39 36 37 37 38 39 39 38 37 37

104

CA x 103

[H+] x 104

[Lac"] x 103

n

1—l

Lutetium Lactate

1 2 4 6 8

5.24 7.08 7.78 7.28 6.64

0.212 0.425 0.965 1.687 2.574

0.328 0.571 0.953 1.260 1.523

1547 1344 988 747 592

10 12 14 16 20

5.98 5.41 4.88 4.4? 4.06

3.663 4.935 6.451 8.107 11.245

1.734 1.902 2.009 2.085 2.290

473 385 311 257 204

24

3.72

14.799

2.393

162

[Lac-] x 103 0.3 1.0 2.0 3.0 4.0 6.0 8.0 10.0 12.0 15.0

xJ

1.612 3.685 8.220 I5.O8 24.64 53.02 95.08 153.9 233.6 395.6

xl

Xg x 10"6

2040 2685 3610 4693 5910

0.550 0.810 0.868 0.939 1.009

8670 11760 15390 19383 26310

1.133 1,236 1.352 1.459 1.629

Xj x 10"6

50

IS 62

62 60 59 58 58

105 Yttrium Lactate

CA

X

10^

[H+] x 104

8

4.26 5.43 5.89 5.75 5-32

10 12 14 16

4.65 4.40 4.13

1 2 4 6

20

24 28 32 38

[Lac-J x 103 0.3 1.0 2.0 3.0 4.0 6.0 8.0 10.0 12.0 15.0 18.0 22.0 26.0 30.0 34.0

4.95 3.78

3.55 3.26 3.12

3.40

XJ

1.330 2.255

4.012

6.339 9.287 17.33 28.59 43.39

62.10 98.66

147.0 233.0

350.0 495.7

677.4

[Lac-] x 103

0.318 0.633 1.367 2.227 3.313 4.532 5.854 7.273 8.907 12.251 15.719

19.199 22.930 28.508

X1

1100 1255 1506 1780 2072

11

0.277 0.478

0.806

1.087

1.305 1.491

1.653 1.782

n/[Lac 871

755 590 488 394 329 282 246

1.877

211 166

2.159 2.285 2.349 2.451

137

2.032

%2 % 10~3

119

102.4 86.0

Xj x 10

200 215 233 24? 258

9.2 9.5 9.5

2722 3449

280 301 320

6511

338 365

8111 10545 13423 16490

432 476

9.4

515 555

9.7 9.7

4239 5092

19894

393

9.4 9-3

9.3 9.7