Calorimetry, titration

Titration calorimetry is a method in which one reactant inside a calorimetric vessel is titrated with another delivered from a burette at a controlled rate. This technique has been adapted to a variety of calorimeters, notably of the isoperibol and heat flow types [194-198]. The output of a titration calorimetric experiment is usually a plot of the temperature change or the heat flow associated with the reaction or physical interaction under study as a function of time or the amount of titrant added. 

A primary use of titration calorimetry is the determination of enthalpies of reaction in solution. The obtained results may of course lead to enthalpies of formation of compounds in the standard state by using appropriate thermodynamic cycles and auxiliary data, as described in chapter 8 for reaction-solution calorimetry. Moreover, when reactions are not quantitative, both the equilibrium constant and the enthalpy of reaction can often be determined from a single titration run [197-206], This also yields the corresponding ArG° and ATS° through equations 2.54 and 2.55. 

Extensive use has been made of titration calorimetry as an analytical tool. These applications, which are outside the scope of this book, have been covered in various reviews [194,197,198,203,204,207], 

The historical development of titration calorimetry has been addressed by Grime [197]. The technique is credited to have been born in 1913, when Bell and Cowell used an apparatus consisting of a 200 cm3 Dewar vessel, a platinum stirrer, a thermometer graduated to tenths of degrees, and a volumetric burette to determine the end point of the titration of citric acid with ammonia lfom a plot of the observed temperature change against the volume of ammonia added [208]. The capabilities of titration calorimetry have enormously evolved since then, and the accuracy limits of modern titration calorimeters are comparable to those obtained in conventional isoperibol (chapter 8) or heat-flow instruments (chapter 9) [195,198], 

The titration procedures described in the literature can be classified as continuous or incremental, depending on the mode of titrant addition. In the first case the titrant is continuously introduced in the reaction vessel at a programmed (not necessarily constant) rate during a run. The application of this method requires apparatus with quick response to temperature changes and can be used only to study fast reactions. Slow reactions (i.e., those with a reaction time longer than the equilibrium time of the reaction vessel) may be accurately studied by the 

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Oscarson J L, Izatt R M, Hill J O and Brown P R 1994 Continuous titration calorimetry Solution Calorimetry, Experimental Thermodynamicsyo IV, ed K N Marsh and PAG O Hare (Oxford Blackwell)... 

Table 5 Binding of palmatine to homo and hetero polymer of AT as revealed from isothermal titration calorimetry [176]...

Fig. 14 Isothermal titration calorimetry for the binding of berberine (a and d) and pal-matine (b and e) to tRNA. Reprinted from [214] with permission from Elsevier...

Alkaloids Spectrophotometry Spectrofluorimetry Isothermal titration calorimetry ... 

Ion transfer, 14 (1977) 1 Irinotecan, anticancer agent, 34 (1997) 68 Isothermal titration calorimetry, in drug design, 38 (2001) 309... 

Instrumentation. H and NMR spectra were recorded on a Bruker AV 400 spectrometer (400.2 MHz for proton and 100.6 MHz for carbon) at 310 K. Chemical shifts (< are expressed in ppm coupling constants (J) in Hz. Deuterated DMSO and/or water were used as solvent chemical shift values are reported relative to residual signals (DMSO 5 = 2.50 for H and 5 = 39.5 for C). ESl-MS data were obtained on a VG Trio-2000 Fisons Instruments Mass Spectrometer with VG MassLynx software. Vers. 2.00 in CH3CN/H2O at 60°C. Isothermal titration calorimetry (ITC) experiments were conducted on a VP isothermal titration calorimeter from Microcal at 30°C. 

Ways are discussed of measuring both compositions and heats of formation fi.e.. excess enthalpies) of two conjugate phases in model amphiphile/water systems by isoperibol titration calorimetry. Calorimetric and phase-volume data are presented for n-C H OH/water at 30... 

LaLonde, J.M., Levenson, M.A., Roe,J.J., Bemlohr, D.A. and Banaszak, L.J. (1994) Adipocyte lipid-binding protein complexed with arachidonic acid titration calorimetry and X-ray crystallographic studies. Journal of Biological Chemistry 269, 25339-25347. 

This is a deceptively simple question to ask, but one which is quite hard to answer. We have performed titration calorimetry experiments (unpublished) intended to determine the enthalpy of reaction for the reaction of aqueous formaldehyde with polypeptides or proteins, without success. In our experiments, the enthalpy of mixing was much larger than that which could be... 

T. K. Dam and C. F. Brewer, Thermodynamic studies of lectin-carbohydrate interactions by isothermal titration calorimetry, Chem. Rev., 102 (2002) 387 -29. 

Further experiments focused therefore on [RuCl(en)(r 6-tha)]+ (12) and [RuCl(rj6-p-cym)(en)]+ (22), which represent the two different classes, and their conformational distortion of short oligonucleotide duplexes. Chemical probes demonstrated that the induced distortion extended over at least seven base pairs for [RuCl(rj6-p-cym)(en)]+ (22), whereas the distortion was less extensive for [RuCl(en)(rj6-tha)]+ (12). Isothermal titration calorimetry also showed that the thermodynamic destabilization of the duplex was more pronounced for [RuCl(r 6-p-cym)(en)]+ (22) (89). DNA polymerization was markedly more strongly inhibited by the monofunctional Ru(II) adducts than by monofunctional Pt(II) compounds. The lack of recognition of the DNA monofunctional adducts by HMGB1, an interaction that shields cisplatin-DNA adducts from repair, points to a different mechanism of antitumor activity for the ruthenium-arenes. DNA repair activity by a repair-proficient HeLa cell-free extract (CFE) showed a considerably lower level of damage-induced DNA repair synthesis (about six times) for [RuCl(en)(rj6-tha)] + compared to cisplatin. This enhanced persistence of the adduct is consistent with the higher cytotoxicity of this compound (89). 

Zeitner, W. A., E. C. Yost, M. L. Machesky, M. I. Tejedor-Tejedor, and M. A. Anderson (1986), "Characterization of Anion Binding on Goethite Using Titration Calorimetry and Cylindrical Internal Reflec-tion-Fourier Transform Infrared Spectroscopy", in J. A. Davis and K. F. Hayes, Eds., Geochemical Processes at Mineral Surfaces, Am. Chem. Soc., Washington, 142-161. 

Characterization of Anion Binding on Goethite Using Titration Calorimetry and Cylindrical Internal Reflection-Fourier Transform Infrared Spectroscopy... 

Titration calorimetry and cylindrical internal reflection-Fourier transform infrared (CIR-FTIR) spectroscopy are two techniques which have seldom been applied to study reactions at the solid-liquid interface. In this paper, we describe these two techniques and their application to the investigation of salicylate ion adsorption in aqueous goethite (a-FeOOH) suspensions from pH 4 to 7. Evidence suggests that salicylate adsorbs on goethite by forming a chelate structure in which each salicylate ion replaces two hydroxyls attached to a single iron atom at the surface. 

To put things into perspective, we. can broadly classify these analytical methods into bulk, dry surface, and in situ interfacial techniques. This chapter focuses on the last category, illustrating two in situ techniques used to study anion binding at the goethite (a-FeOOH)-water interface titration calorimetry and cylindrical internal reflection-Fourier transform infrared (CIR-FTIR) spectroscopy. In fact, CIR-FTIR could prove to be extremely powerful, since it allows direct spectroscopic observation of ions adsorbed at the mineral-water interface. 

Titration calorimetry involves the measurement of heat evolved while adding a titrant. This technique is well established for determining reaction enthalpies in homogeneous solution (see refs. 15 and 16 for general reviews of the method) but has been used far less often to measure adsorption enthalpies in heterogeneous suspensions. Instead, adsorption studies have relied mainly on the... 

It may prove possible to apply titration calorimetry data in one further direction. If AG can be estimated for SAL-goethite complexation and reaction enthalpies can be obtained under equilibrium conditions, then an entropy change for this reaction can also be derived. This can only be done, however, if the adsorption reaction can be shown to be reversible. Since this has not been proven as yet in our systems, such thermodynamic extensions of titration calorimetry can only be speculative at this time. 

Eatough, D.J. Christensen, J.J. Izatt, R.M. "Experiments in Thermometric Titrimetry and Titration Calorimetry" Brigham Young Univ. Press Provo, UT, 1974. 

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