FACULTAD DE QUÍMICA

DEPARTAMENTO DE QUÍMICA ANALÍTICA

5622-37-54; 622-37-02; FAX 548 32 27
Dr. ALAIN QUERE T., Profesor

MAESTRÍA EN QUÍMICA
EQUILIBRIOS EN DISOLUCIÓN I

PROGRAMA DEL CURSO

OBJETIVO GENERAL
Estudiar a profundidad los equilibrios químicos en disolución y las bases teóricas de la
complejometría para introducir al estudiante en los métodos de investigación en estos campos.
Para lograr este objetivo, el estudiante:
1. Aplicará sus conocimientos de computación realizando programas de cálculo para representar
gráficamente las variables de concentración de especies químicas en disolución.
2. Analizará y discutirá en forma crítica los métodos y técnicas de análisis químicos
complejométricos, con base en los conocimientos avanzados de los equilibrios químicos en
disolución.
3. Propondrá algunos procedimientos metodológicos y experimentales apropiados al estudio de
diferentes tipos de equilibrios químicos en disolución.

CONTENIDO
I. ESTUDIO TEÓRICO AVANZADO DE LOS EQUILIBRIOS EN DISOLUCIÓN
1. Equilibrios de formación de compuestos de coordinación.
2. Métodos gráficos variados de representación de los equilibrios en disolución.
3. Influencias mutuas de los equilibrios ácido-base y de formación de compuestos de coordinación.
4. Función de formación de Bjerrum.
5. Compuestos de coordinación mono y polinucleares.
6. Compuestos de coordinación mixtos.

II. INTRODUCCIÓN A LA METODOLOGÍA DE DETERMINACIÓN DE CONSTANTES DE

EQUILIBRIO EN DISOLUCIÓN
1. Métodos experimentales usuales y metodología apropiada.
2. Estudio de algunos métodos y técnicas experimentales.
-Potenciométricos.
-Polarográficos.
-Espectrofotométricos.

TÉCNICAS DE ENSEÑANZA
Exposición oral por parte del profesor, seminarios presentados por los estudiantes, discusiones
dirigidas.
Análisis de bibliografía original y preparación de resúmenes, elaboración de proyectos
computacionales individuales o en equipo.

EVALUACIÓN
Evaluación de la participación de los estudiantes en las clases, de los proyectos, de los seminarios y
resúmenes. El promedio de calificación obtenido en los proyectos computacionales se tomará como
calificación final de la materia.

BIBLIOGRAFÍA
J. N. BUTLER, David R. Cogley, Ionic Equilibrium: Solubility and pH Calculations, Wiley, 1998

SANTIAGO VICENTE PEREZ Química de las Disoluciones: Diagramas y Cálculos Gráficos

Alhambra, Madrid, 1979. (QD75 V5, FQA)

BURRIEL MARTI F., F. LUCENA CONDE, S. ARRIBAS JIMENO, J. HERNANDEZ MENDEZ,

Química Analítica Cualitativa, 11a ed., Paraninfo, Madrid, 1983. (QD81 B72, FQA)

SILLEN L.G. Graphic Presentation of Equilibrium Data. en Treatise on Analytical Chemistry, I.M.
KOLTHOFF, P.J. ELVING eds., Part I, Vol. I, Chap. 8. Interscience, New york, 1959. (Ser., FQA)

HOGFELDT E. Graphic Presentation of Equilibrium Data, en I.M. KOLTHOFF AND P.J. ELVING
Eds., Treatise on Analytical Chemistry, Part I, vol 2, Chap. 15, Wiley, 1984. (QD75 K62, Ser., FQB)

W.B. GUENTHER, Chemical Equilibrium, Plenum, New-York, 1975 (QD503 G84, FQA)

W.B. GUENTHER, Unified Equilibrium Calculations, Wiley, New-York, 1991 (QD503 G843, FQA)

F. R. HARTLEY, C. BURGESS, R. M. ALCOCK, Solution Equilibria, Ellis Horwood, Chichester,

1980 (QD503 H33, FQB)

S. KOTRLY, SUCHA L., Handbook of Chemical Equilibria in Analytical Chemistry Ellis-Horwood,

Chichester, 1985 (QD78 K6 Ser., FQB)

L. SUCHA, S. KOTRLY Solution Equilibria in Analytical Chemistry, Van Nostrand Reinhold,

London 1972

RINGBOM A., Complexation in Analytical Chemistry Wiley, 1963. (QD111 R5, Ser., FQB) Versión
española: Formación de Complejos en Química Analítica Alahambra, Madrid, 1979.

A. RINGBOM, E. WANNINEN, Complexation Reactions, en I.M. KOLTHOFF and P.J. ELVING,

Treatise on Analytical Chemistry, Part I, Vol. 2, Chap. 20., Wiley, 1984.(QD75 K62, Ser., FQB)

J. INCZEDY, Analytical Applications of Complex Equilibria Ellis Horwood, 1976. (QD77 I52, Ser.,
FQB y FQA)
A. JOHANSSON, E. WANNINEN, Titrimetry: Complexation Titration, en I.M. KOLTHOFF AND
P.J. ELVING Eds. Treatise on Analytical Chemistry, Part I, Vol. 11, Chap. 117, Interscience, 1975.
(IQ UNAM)
H. ROSSOTTI, The Study of Chemical Equilibrium, Longman, 1978.

C.F. BAES, R.E. MESMER, The Hydrolysis of Cations. Wiley, 1976. (QD501 B268, FQB)

E.P. SERJEANT, Potentiometry and Potentiometric Titrations Wiley, New York, 1984. (QD115 S47
Ser., FQB)

D.D. PERRIN, Masking and Demasking in Analytical Chemistry, Treatise on Analytical Chemistry,
Part I, vol. 2, 2nd Ed., Cap. 21; I.M. KOLTHOFF, P.J. ELVING Eds., Wiley, New York, 1979.
(QD75 K62 Ser., FQB)

Z. HOLZBECHER, M. KRAL, L. DIVIS, L. SUCHA, F. VLACIL, , Handbook of Organic Reagents

in Inorganic Analysis Ellis-Horwood Chichester, 1976 (QD77 H35 Ser., FQB)

BUDEVSKY O., Foundations of Chemical Analysis. Ellis-Horwood, Chichester, 1979. (QD 75.2
B82; FQA)

SCHWARZENBACH G., H. FLASCHKA, Complexometric Titration Methuen, London, 1969.

(QD111 S45, FQB)

A. ALBERT, E.P. SERJEANT, The Determination of Ionization Constants: A laboratory Manual,

Chapman and Hall, London, 1984, 3a Ed. (QD561 A 37 Ref., FQB)

J. N. BUTLER, Ionic Equilibrium: A Mathematical Approach Addison-Wesley, Reading

Massachusetts, 1964 (QD561 B9, FQA)

G. M. FLECK, Equilibria in Solution (QD541 F54, FQA) Holt Rinehart and Winston, New York,
1966 Equilibrios en Disolución, Alhambra, Madrid, 1967

G. SVEHLA, Automatic Potentiometric Titrations. Ser. Anal. Chem. V. 60. Pergamon Oxford 1978
(s/c, FQB)

R. PRIBIL, Analytical Application of EDTA and Related Compounds. Ser. Anal. Chem., Vol. 52,
Pergamon Oxford 1972 (s/c, FQB)

I.M. KOLTHOFF, E.B. SANDELL, E.J.MEEHAN, S. BRUCKENSTEIN, Quantitative Chemical

Analysis, Mac Millan, New York 1969 (QD101 Q82, FQA y FQB)
BIBLIOGRAFIA ADICIONAL
DIAGRAMAS LOGARITMICOS Y APLICACIONES.

JOHANSSON A., Logarithmic Diagrams and Gran-Curves as an Aid in Potentiometric Titrations in Complexometry.
Talanta, 20, 89-102 (1973).
WANNINEN E., Logarithmic Diagrams in Acid-Base Titrations and Estimation of Titration Errors. Talanta, 29-32
(1980).
MACCA C., G. GIORGIO BOMBI Symmetry Properties of Potentiometric Titration Curves. J. Chem. Educ., 60, 1026-
30 (1983).

JOHANSSON S., Logarithmic Diagrams as an Aid in Complexometric Titrations where 1:2 or 2:1 as well as 1:1
Metal-Ligand Complexes are Regarded as Principal Species. Talanta, 28, 241-49 (1981).

NONOVA D., N. LIHAREVA, On the Copper(II)-EDTA-PAR System for Visual and Photometric End-Point Detection
in Iron(III)-EDTA Titrations. Talanta, 23, 439-43 (1976).

BUDEVSKY O., Graphical Method for Construction of Titration Curves. En Analytical Chemistry: Essays in Memory
of Anders Ringbom, E. WANNINEN ed. Pergamon, Oxford, 1977.

JOHANSSON A., F. INGMAN, Photometric Titrations. En Analytical Chemistry: Essays in Memory of Anders
Ringbom, E. WANNINEN ed. Pergamon, Oxford, 1977

INGMAN F., E. STILL, The Precision of Photometric and Potentiometric Measurements and Titrations, íParticularly
Gran Titrations. En Analytical Chemistry: Essays in Memory of Anders Ringbom, E. WANNINEN ed. Pergamon,
Oxford, 1977.

TABBUTT F.D., Titration Curves from Logarithmic Concentration Diagrams. J. Chem. Educ., 43, 245-49 (1966).

YINGST A., Evaluation of Titration Analysis with Logarithmic Concentration Diagrams. J. Chem. Educ., 44, 601-603
(1967).

FREISER H., Q. FERNANDO, Teaching Ionic Equilibrium. Use of log-chart transparencies. J.Chem. Educ., 42, 35-38
(1965).

LEVIE R., de Ratio Diagrams. A simple graphical Representation of Complicated Equilibria. J. Chem. Educ., 47, 187-
92 (1970).

FORMACION DE COMPUESTOS DE COORDINACION

FRAUSTO DA SILVA J.J.R., The Chelate Effect Redefined. J. Chem. Educ., 60, 390-92 (1983).

CHUNG-SUN CHUNG, Entropy Effects in Chelation Reactions. J. Chem. Educ., 61, 1062-64 (1984).

COLEMAN E.M., A.G. SHARPE, A Simple Illustration of the Effect of the Solvent on the Relative Stabilities of Metal
Complexes. J. Chem. Educ., , 980 (198 ).

CHUNG-SUN CHUNG, Statistical Factors in Complexation Reactions. J. Chem. Educ., 62, 107 (1985).
COMPLEJOS MIXTOS
BURGER K., On the Selectivity and Analytical Importance of the Formation of Mixed Ligand Complexes. En
Analytical Chemistry: Essays in Memory of Anders Ringbom, E. WANNINEN ed. Pergamon, Oxford, 1977.

GALUS M., HULANICKI A., Spectrophotometric Study of Mixed Copper Complexes with Bis(Carboxymethyl)-
Dithiocarbamate and Ligands Containing Donor Atoms. En Analytical Chemistry: Essays in Memory of Anders
Ringbom, E. WANNINEN ed. Ligand Complexes. Pergamon, Oxford, 1977.

PERRIN D.D., The Formation and Stability of Mixed Ligand Complexes. En Analytical Chemistry: Essays in Memory
of Anders Ringbom, E. WANNINEN ed. Pergamon, Oxford, 1977.

TEDESCO P.H., MARTINEZ J., Polarographic Study of Simple and Mixed-Ligand Complex Formation. Talanta, 31,
155-161, 1984.

TANAKA M., Multidentate Ligand Substitution Reactions as Applied to Analytical Chemistry. En Analytical
Chemistry: Essays in Memory of Anders Ringbom, E. WANNINEN ed., Pergamon, Oxford, 1977.

TITULACIONES COMPLEJOMETRICAS
KEIHEI UENO, Guide for Selecting Conditions of EDTA Titrations. J. Chem. Educ.,

REILLEY C.N., R.W. SCHMID, Principles of End-Point Detection in Chelometric Titrations Using Metallochromic
Indicators. Anal. Chem., 31, 887-97 (1959).

H. FREISER, FERNANDO Q., Ionic Equilibria in Analytical Chemistry. Wiley, New-York, 1963.

BUTLER J.N., Ionic Equilibrium. Addison-Wesley, Reading, 1964.

MARTELL A.E., Chelating Agents for Metal Buffering and Analysis in Solution. Pure & Appl. Chem., 50, 813-29
(1978).

STUMM W., J.J. MORGAN, Aquatic Chemistry. An introduction emphasising chemical equilibria in natural waters.
2nd ed. Wiley, New-york, 1981. (QD 142 S87; FQA)

KIELLAND J., Individual Activity Coefficients of Ions in Aqueous Solutions. J. Amer. Chem. Soc. 59, 1675-78 (1937).
TANAKA M., NAKAGAWA G., General Considerations in Compleximetric Titrations. Anal. Chim. Acta, 32, 123-38
(1965).

IRVING H.M.N.H., Coordination Compounds in Analytical Chemistry. Pure & Appl. Chem., 50, 1129-46 (1978).

TEMAS SELECTOS
LEHN J.M., Cryptates: Inclusion Complexes of Macropolycyclic Receptor Molecules. Pure & Appl. Chem., 50, 871-92
(1978).

FORSLING W., HIETANEN S., SILLEN L.G., Studies on the Hydrolysis of Metal Ions. III. The hydrolysis of the
mercury(I) Ion, Hg22+.Acta Chem. Scand., 6, 901-909 (1952).

SILLEN L.G., On Equilibria in Systems with Polynuclear Complex Formation. I. Methods for deducing the
Composition of the Complexes from Experimental Data. "Core + Links" Complexes. Acta Chem. Scand. 8, 299-317
(1954).

SILLEN L.G., On Equilibria in Systems with Polynuclear Complex Formation. II. Testing Simple Mechanisms which
give "Core + Links" Complexes of Composition B(AtB)n . Acta Chem. Scand., 8, 318-335 (1954).
SILLEN L.G., Some Recent Results on Hydrolytic Equilibria. Pure & Appl. Chem., 17, 55-78 (1968).

KRAGTEN J., Manipulations, pM'-pH Diagrams and Accuracy in Determination of Metals. Talanta, 24, 483-90
(1977).

F. L. HAHN, pH und Potentiometrische Titrierungen Akademische Verlagsgesellschaft, Frankfurt 1964. (QD 81 H3;
FQA)

MARK AND RECHNITZ, Kinetic in Analytical Chemistry Interscience, New York 1968. (QD 75 M287; FQA)

PRINCIPIOS Y METODOS DE DETERMINACION DE CONSTANTES DE EQUILIBRIO.

FROANAEUS S., A New Principle for the Investigation of Complex Equilibria and the Determination of Complexity
Constants. Acta Chem. Scand., 4, 72-87 (1950).

DeFORD D.D., D.N. HUME, The Determination of Consecutive Formation Constants of Complex Ions from
Polarographic Data. J. Amer. Chem. Soc., 73, 5321-25 (1951).

COOKSON R.F., The Determination of Acidity Constants. Chemical Reviews, 74, 5-28 (1974).
McBRIDE W.A.E., Talanta Review. Spectrophotometric Determination of Equilibrium Constants in Solution. Talanta,
21, 979-1004 (1974).

RAMAMURTI G., K. RENGANATHAN, The Instability Constant of the I 3- === I- + I2 System. A student L.R.
GANESAN experiment. J. Chem. Educ., 53, 326-27 (1976).

BECK M.T., Determination of Stability Constants of Metal Complexes. En Analytical Chemistry: Essays in Memory of
Anders Ringbom, E. WANNINEN ed. Pergamon, Oxford, 1977.

GAIZER F. *Computer Evaluation of Complex Equilibria. Coord. Chem. Reviews, 27, 195-222 (1979).

LEE HIN-FAT, HIN-CHEUNG LEE, A Method for the Determination of Stability Constants of Unstable Complexes. J.
Chem. Educ., 61, 925-26 (1984).

RAMETTE R.W. Metal-Ligand Complexes - A Calculation Challenge. J. Chem. Educ.,

A. E. MARTELL, R. J. MOTEKAITIS, Determination and Use of Stability Constants VCH New York, 1988

RECOPILACIONES DE CONSTANTES DE EQUILIBRIO

L. G. SILLEN, A. E. MARTELL, Stability Constants of Metal Ion Complexes, 2nd Ed. The Chemical Society London
1964. ( IQ UNAM)

idem + E. HOGFELDT , R. M. SMITH Supplement No1, Special Publication No 25 The Chemical Society London
1971 (QD501 C43 Ser., FQB)

G. KORTUM, W. VOGEL, K. ANDRUSSOW, Dissociation Constants of Organic Acids in Aqueous Solution

Butterworth, London 1961. ( IQ UNAM)

D. D. PERRIN, Dissociation Constants of Organic Bases in Aqueous Solution Butterworth, London 1965.

E. P, SERJEANT, B. DEMPSEY, Ionization Constants of Organic Acids in Aqueous Solution IUPAC Chem. Data
Series No 23, Pergamon Oxford 1979. (s/c, FQB)
E. HOGFELDT, Stability Constants of Metal-Ion Complexes, Part A Inorganic Ligands IUPAC Chem. Data Series No
21, Pergamon Oxford 1982 (QD561 H63, Ser., FQB)

D. D. PERRIN, Stability Constants of Metal-Ion Complexes, Part B Organic Ligands IUPAC Chem. Data Series No
22, Pergamon Oxford 1983. (QB503 S82, Ser., FQB)

A. E. MARTELL, R. M. SMITH, Critical Stability Constants, Vol 1 - 6, Plenum Press, New York 1974-82. (QD503
M37 Ref., FQA y FQB)

ACTIVIDAD Y COEFICIENTES DE ACTIVIDAD

E.A GUGGENHEIM, Phil. Mag., 1935, 19, 588

K.S. PITZER, J. Phys. Chem., 1973, 77, 268

K.S. PITZER, G. MAYORGA, J. Phys. Chem., 1973, 77, 2300

M. MELOUN, S. KOTRLY, Collec. Czech. Chem. Commun., 1977, 42, 2115

CALIBRACION DEL MEDIDOR DE pH

L.G. SILLEN, G. BIEDERMANN, Arkiv Kemi, 1953, 5, 425

BIBLIOGRAFIA RELACIONADA
J'OM BOCKRIS, A.K.N. REDDY, Modern Electrochemistry Vol. 1 Plenum, New York, 1973 (QD553 B62, FQA, FQB)

J. BURGESS Metal Ions in Solution Ellis Horwood, Chichester, 1978 (QD561 B86, FQB)

TANAKA M., Multidentate Ligand Substitution Reactions as Applied to Analytical Chemistry. En Analytical
Chemistry: Essays in Memory of Anders Ringbom, E. WANNINEN ed., Pergamon, Oxford, 1977. (IMP)

IRVING H.M.N.H., Coordination Compounds in Analytical Chemistry. Pure & Appl. Chem., 50, 1129-46 (1978).
(FQB, IQ UNAM)