Titration example

Many pharmaceutical compounds are weak acids or bases that can be analyzed by an aqueous or nonaqueous acid-base titration examples include salicylic acid, phenobarbital, caffeine, and sulfanilamide. Amino acids and proteins can be analyzed in glacial acetic acid, using HCIO4 as the titrant. For example, a procedure for determining the amount of nutritionally available protein has been developed that is based on an acid-base titration of lysine residues. ... 

Calculate the pH at any point in a strong base-strong acid, strong base-weak acid, and weak base-strong acid titration, Examples 11.5, 11.6, 11.7, and 11.8. 

Biamperometry — Whereas in amperometry the -> current is limited by the electrode process proceeding at one indicator electrode (and the -> counter electrode has no effect), in biamperometry the current flowing between two indicator electrodes is measured, i.e., both electrodes can limit the overall current. This approach is useful in following some -> titrations, and it may lead to zero current (dead-stop) at the equivalence point (dead-stop titration). Example iodine in an iodide solution is titrated with As(III). Two platinum electrodes with a potential difference of around 100 mV prompt iodine to be reduced on one electrode and iodide being oxidized at the other. The two processes maintain an almost constant current until the endpoint when iodine is exhausted. 

Types of Titration Examples of Reaction Suitable Indicator pH Range of Colour Change... 

Consider again our titration example (p. 63). If we had only the alkalinity reported as CaCCV , we would have to convert this back to milliequivalents per liter or moles per liter by reversing the calculation ... 

Many acid-base indicators are plant pigments. For example, by boiling chopped red cabbage in water we can extract pigments that exhibit many different colors at various pHs (Figure 16.6). Table 16.1 lists a number of indicators commonly used in acid-base titrations. The choice of a particular indicator depends on the strength of the acid and base to be titrated. Example 16.7 illustrates this point. 

Continuing with the titration example, suppose that we wish to obtain an estimate of the concentration with a precision of 0.1%. How many replicate titrations should we perform ... 

Much of the remainder of this book will deal with the evaluation of random errors, which can be studied by a wide range of statistical methods. In many cases we shall assume for convenience that systematic errors are absent (though methods which test for the occurrence of systematic errors will be described). But first we must discuss systematic errors in more detail - how they arise, and how they may be countered. The titration example above shows that systematic errors cause the mean value of a set of replicate measurements to deviate from the true value. It follows that (a) in contrast to random errors, systematic errors cannot be revealed merely by making repeated measurements, and that (b) unless the true result of the analysis is known in advance - an unlikely situation - very large systematic errors might occur, but go entirely undetected unless suitable precautions are taken. In other words, it is all too easy to overlook substantial sources of systematic error. A few examples will clarify both the possible problems and their solutions. 

In the remainder of this chapter, we shall choose our acid-base titration examples in some pharmacopeias, especially the european one. Indeed, most of the pharmacologically active chemical products (about 85%) do possess one or several acidic-basic sites due to the presence of some kinds of functional groups. 

Equilibrium aspects of acid-base reactions, including calculations and discussion of changes in pH during acid-base titrations. Examples of solubility product calculations. 

Standardizing a solution of an oxidizing agent through a redox titration—Example 5-10 illustrated... 

One can write acid-base equilibrium constants for the species in the inner compact layer and ion pair association constants for the outer compact layer. In these constants, the concentration or activity of an ion is related to that in the bulk by a term e p(-erp/kT), where yp is the potential appropriate to the layer [25]. The charge density in both layers is given by the algebraic sum of the ions present per unit area, which is related to the number of ions removed from solution by, for example, a pH titration. If the capacity of the layers can be estimated, one has a relationship between the charge density and potential and thence to the experimentally measurable zeta potential [26]. 

Figure V-8 illustrates that there can be a pH of zero potential interpreted as the point of zero charge at the shear plane this is called the isoelectric point (iep). Because of specific ion and Stem layer adsorption, the iep is not necessarily the point of zero surface charge (pzc) at the particle surface. An example of this occurs in a recent study of zircon (ZrSi04), where the pzc measured by titration of natural zircon is 5.9 0.1...

The saturation coverage during chemisorption on a clean transition-metal surface is controlled by the fonnation of a chemical bond at a specific site [5] and not necessarily by the area of the molecule. In addition, in this case, the heat of chemisorption of the first monolayer is substantially higher than for the second and subsequent layers where adsorption is via weaker van der Waals interactions. Chemisorption is often usefLil for measuring the area of a specific component of a multi-component surface, for example, the area of small metal particles adsorbed onto a high-surface-area support [6], but not for measuring the total area of the sample. Surface areas measured using this method are specific to the molecule that chemisorbs on the surface. Carbon monoxide titration is therefore often used to define the number of sites available on a supported metal catalyst. In order to measure the total surface area, adsorbates must be selected that interact relatively weakly with the substrate so that the area occupied by each adsorbent is dominated by intennolecular interactions and the area occupied by each molecule is approximately defined by van der Waals radii. This... 

The procedure is computationally efficient. For example, for the catalytic subunit of the mammalian cAMP-dependent protein kinase and its inhibitor, with 370 residues and 131 titratable groups, an entire calculation requires 10 hours on an SGI 02 workstation with a 175 MHz MIPS RIOOOO processor. The bulk of the computer time is spent on the FDPB calculations. The speed of the procedure is important, because it makes it possible to collect results on many systems and with many different sets of parameters in a reasonable amount of time. Thus, improvements to the method can be made based on a broad sampling of systems. 

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. 

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. 

Analytical chemistry is often described as the area of chemistry responsible for characterizing the composition of matter, both qualitatively (what is present) and quantitatively (how much is present). This description is misleading. After all, almost all chemists routinely make qualitative or quantitative measurements. The argument has been made that analytical chemistry is not a separate branch of chemistry, but simply the application of chemical knowledge. In fact, you probably have performed quantitative and qualitative analyses in other chemistry courses. For example, many introductory courses in chemistry include qualitative schemes for identifying inorganic ions and quantitative analyses involving titrations. 

The accuracy of a standardization depends on the quality of the reagents and glassware used to prepare standards. For example, in an acid-base titration, the amount of analyte is related to the absolute amount of titrant used in the analysis by the stoichiometry of the chemical reaction between the analyte and the titrant. The amount of titrant used is the product of the signal (which is the volume of titrant) and the titrant s concentration. Thus, the accuracy of a titrimetric analysis can be no better than the accuracy to which the titrant s concentration is known. 

A simple example of a titration is an analysis for Ag+ using thiocyanate, SCN , as a titrant. 

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. 

When a suitable reaction involving the analyte does not exist it may be possible to generate a species that is easily titrated. Eor example, the sulfur content of coal can be determined by using a combustion reaction to convert sulfur to sulfur dioxide. 

To find the end point we monitor some property of the titration reaction that has a well-defined value at the equivalence point. Eor example, the equivalence point for a titration of ITCl with NaOlT occurs at a plT of 7.0. We can find the end point. 

The titration curve in Figure 9.1 is not unique to an acid-base titration. Any titration curve that follows the change in concentration of a species in the titration reaction (plotted logarithmically) as a function of the volume of titrant has the same general sigmoidal shape. Several additional examples are shown in Figure 9.2. 

Concentration is not the only property that may be used to construct a titration curve. Other parameters, such as temperature or the absorbance of light, may be used if they show a significant change in value at the equivalence point. Many titration reactions, for example, are exothermic. As the titrant and analyte react, the temperature of the system steadily increases. Once the titration is complete, further additions of titrant do not produce as exothermic a response, and the change in temperature levels off. A typical titration curve of temperature versus volume of titrant is shown in Figure 9.3. The titration curve contains two linear segments, the intersection of which marks the equivalence point. 

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

Titrating a Weak Acid with a Strong Base For this example let s consider the titration of 50.0 mL of 0.100 M acetic acid, CH3COOH, with 0.100 M NaOH. Again, we start by calculating the volume of NaOH needed to reach the equivalence point thus... 

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