Titration complex

The formation of complexes affects both particle-solvent and particle-particle interactions. The solubility of proteins may be increased by their electrostatic complexing with anionic polysaccharides. Formation of titration-complexes may increase protein solubility and inhibit protein precipitation at the lEP. Anionic polysaccharides can act as protective hydrocoUoids inhibiting aggregation and precipitation of like-charged dispersed protein particles, for example, of denatured proteins. This protective action also can increase the stability of protein suspensions and oil-in-water emulsions stabilized by soluble protein-anionic polysaccharide complexes. 

The titration procedure is very general and can be used for a variety of determinations. Chapters 13 through 17 consider the titration method in more detail. Acid-base titrations, complexation titrations, and precipitation titrations are described. 

Abstract. Crown ethers derived from tartaric acid present a number of interesting features as receptor frameworks and offer a possibility of enhanced metal cation binding due to favorable electrostatic interactions. The synthesis of polycarboxylate crown ethers from tartaric acid is achieved by simple Williamson ether synthesis using thallous ethoxide or sodium hydride as base. Stability constants for the complexation of alkali metal and alkaline earth cations were determined by potentiometric titration. Complexation is dominated by electrostatic interactions but cooperative coordination of the cation by both the crown ether and a carboxylate group is essential to complex stability. Complexes are stable to pH 3 and the ligands can be used as simultaneous proton and metal ion buffers. The low extractibility of the complexes was applied in a membrane transport system which is a formal model of primary active transport. 

At equilibrium both liquid and solid phases were analyzed. Chloride ion content was determined by the Volhard method. H2PO4 ions were precipitated as NH MgPO 6H2O, and the excess of Mg was titrated complex-ometrically (1). Ammonium ions were removed and the excess of base used was titrated with HCl. 

The mixtures were equilibrated for 1-3 days in a thermostat. The ammonium ion content was determined by the Kjeldahl method. The 2 4 was precipitated as NH MgPO, and the exceds magnesium was titrated complex-imetrically. The refractive index was measured with a IRF-22 refractometer. 

Cjrtochrome c. Altschul et al. (24) isolated a soluble enzyme from yeast that could oxidize reduced cytochrome c. They believed at first that they had solubilized cytochrome oxidase, but in later papers (15,25) they reported that H2O2 was required for this oxidation, and named the enz rme cytochrome c peroxidase. They assayed its activity by measuring the rate of oxidation of reduced cytochrome c spectrophotometrically. Chance (93,94), in his study of peroxidase donor specifidly, used reduced cytochrome c as a donor for horseradish peroxidase, verdoperoxidase, and lactoperoxidase, as well as for cytochrome c ]>eroxidase. George (161) recently titrated complex II (from cytochrome c peroxidase and HtOi) with reduced cytochrome c by measuring the changes in optical density at 433 mju. 

Complexometric indicators behave in a similar way to titrating complexing agents such as EDTA. They generally change color with pH, but one species, for example Hln, will react with excess metal ions M" ... 

Recent developments m calorimetry have focused primarily on the calorimetry of biochemical systems, with the study of complex systems such as micelles, protems and lipids using microcalorimeters. Over the last 20 years microcalorimeters of various types including flow, titration, dilution, perfiision calorimeters and calorimeters used for the study of the dissolution of gases, liquids and solids have been developed. A more recent development is pressure-controlled scamiing calorimetry [26] where the thennal effects resulting from varying the pressure on a system either step-wise or continuously is studied. 

Among the complexing agents that find use as titrating agents, ethylenediamine-A,A(A, A-tet-raacetic acid (acronym EDTA, and equation abbreviation, H4Y) is by far the more important, and it is used in the vast majority of complexometric titrations. The successive acid values of H4Y are pKi = 2.0, pisTj = 2.67, = 6.16, pTCt = 10.26 at 20°C and an ionic strength of 0.1. The fraction... 

The more stable the metal complex, the lower the pH at which it can be quantitatively formed. Elements in the first group may be titrated with EDTA at pH 1 to 3 without interference from cations of the last two groups, while cations of the second group may be titrated at pH 4 to 5 without interference from the alkaline earths. 

Direct Titrations. The most convenient and simplest manner is the measured addition of a standard chelon solution to the sample solution (brought to the proper conditions of pH, buffer, etc.) until the metal ion is stoichiometrically chelated. Auxiliary complexing agents such as citrate, tartrate, or triethanolamine are added, if necessary, to prevent the precipitation of metal hydroxides or basic salts at the optimum pH for titration. Eor example, tartrate is added in the direct titration of lead. If a pH range of 9 to 10 is suitable, a buffer of ammonia and ammonium chloride is often added in relatively concentrated form, both to adjust the pH and to supply ammonia as an auxiliary complexing agent for those metal ions which form ammine complexes. A few metals, notably iron(III), bismuth, and thorium, are titrated in acid solution. 

BackTitrations. In the performance of aback titration, a known, but excess quantity of EDTA or other chelon is added, the pH is now properly adjusted, and the excess of the chelon is titrated with a suitable standard metal salt solution. Back titration procedures are especially useful when the metal ion to be determined cannot be kept in solution under the titration conditions or where the reaction of the metal ion with the chelon occurs too slowly to permit a direct titration, as in the titration of chromium(III) with EDTA. Back titration procedures sometimes permit a metal ion to be determined by the use of a metal indicator that is blocked by that ion in a direct titration. Eor example, nickel, cobalt, or aluminum form such stable complexes with Eriochrome Black T that the direct titration would fail. However, if an excess of EDTA is added before the indicator, no blocking occurs in the back titration with a magnesium or zinc salt solution. These metal ion titrants are chosen because they form EDTA complexes of relatively low stability, thereby avoiding the possible titration of EDTA bound by the sample metal ion. 

In a back titration, a slight excess of the metal salt solution must sometimes be added to yield the color of the metal-indicator complex. Where metal ions are easily hydrolyzed, the complexing agent is best added at a suitable, low pH and only when the metal is fully complexed is the pH adjusted upward to the value required for the back titration. In back titrations, solutions of the following metal ions are commonly employed Cu(II), Mg, Mn(II), Pb(II), Th(IV), and Zn. These solutions are usually prepared in the approximate strength desired from their nitrate salts (or the solution of the metal or its oxide or carbonate in nitric acid), and a minimum amount of acid is added to repress hydrolysis of the metal ion. The solutions are then standardized against an EDTA solution (or other chelon solution) of known strength. 

Manganese(II) can be titrated directly to Mn(III) using hexacyanoferrate(III) as the oxidant. Alternatively, Mn(III), prepared by oxidation of the Mn(II)-EDTA complex with lead dioxide, can be determined by titration with standard iron(II) sulfate. 

Probably the most extensively applied masking agent is cyanide ion. In alkaline solution, cyanide forms strong cyano complexes with the following ions and masks their action toward EDTA Ag, Cd, Co(ll), Cu(ll), Fe(ll), Hg(ll), Ni, Pd(ll), Pt(ll), Tl(lll), and Zn. The alkaline earths, Mn(ll), Pb, and the rare earths are virtually unaffected hence, these latter ions may be titrated with EDTA with the former ions masked by cyanide. Iron(lll) is also masked by cyanide. However, as the hexacy-anoferrate(lll) ion oxidizes many indicators, ascorbic acid is added to form hexacyanoferrate(ll) ion. Moreover, since the addition of cyanide to an acidic solution results in the formation of deadly... 

Masking by oxidation or reduction of a metal ion to a state which does not react with EDTA is occasionally of value. For example, Fe(III) (log K- y 24.23) in acidic media may be reduced to Fe(II) (log K-yyy = 14.33) by ascorbic acid in this state iron does not interfere in the titration of some trivalent and tetravalent ions in strong acidic medium (pH 0 to 2). Similarly, Hg(II) can be reduced to the metal. In favorable conditions, Cr(III) may be oxidized by alkaline peroxide to chromate which does not complex with EDTA. 

In resolving complex metal-ion mixtures, more than one masking or demasking process may be utilized with various aliquots of the sample solution, or applied simultaneously or stepwise with a single aliquot. In favorable cases, even four or five metals can be determined in a mixture by the application of direct and indirect masking processes. Of course, not all components of the mixture need be determined by chelometric titrations. For example, redox titrimetry may be applied to the determination of one or more of the metals present. 

Salicylic acid 2-Hydroxybenzoic acid LeSCN2+ at pH 3 is reddish-brown Typical uses Pe(III) titrated with EDTA to colorless iron-EDTA complex... 

This reaction occurs quickly and is of known stoichiometry. A titrant of SCN is easily prepared using KSCN. To indicate the titration s end point we add a small amount of Fe + to the solution containing the analyte. The formation of the red-colored Fe(SCN) + complex signals the end point. This is an example of a direct titration since the titrant reacts with the analyte. 

Unfortunately, it often happens that there is no suitable indicator for this direct titration. Reacting Ca + with an excess of the Mg -EDTA complex... 

A titration in which the analyte displaces a species, usually from a complex, and the amount of the displaced species is determined by a titration. 

Examples of titration curves for (a) a complexation titration, (b) a redox titration, and (c) a precipitation titration. 

The approach that we have worked out for the titration of a monoprotic weak acid with a strong base can be extended to reactions involving multiprotic acids or bases and mixtures of acids or bases. As the complexity of the titration increases, however, the necessary calculations become more time-consuming. Not surprisingly, a variety of algebraic and computer spreadsheet approaches have been described to aid in constructing titration curves. 

A titration in which the reaction between the analyte and titrant is a complexation reaction. 

The utility of complexation titrations improved following the introduction by Schwarzenbach, in 1945, of aminocarboxylic acids as multidentate ligands capable of forming stable 1 1 complexes with metal ions. The most widely used of these new ligands was ethylenediaminetetraacetic acid, EDTA, which forms strong 1 1 complexes with many metal ions. The first use of EDTA as a titrant occurred in... 

A second ligand in a complexation titration that initially binds with the analyte but is displaced by the titrant. 

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