158 We cll the moles of analyte titted fom the moles of rant ‘dod and the ratio in whic they SSTOICHIOMETHIC CALCULATIONS: THE WORKHORSE OF THE ANALYST untreated sample. The dry weight i taken aftr the sample as been died by ete ing, desiccation, or freezedrying. Ifthe test substance i unstable to heat, the s- Dl should not be died by heating, The weight of the ash residue afer the organic Tater as been bummed off i the third basis of weight. This can obviously be used ‘nly for mineral (inorganic) analysis. 54 Volumetric Analysis: How Do We Make Stoichiometric Calculations? Volumetic or tivimettic analyses are among the most useful and accurate analy ical techniques, especialy for milimole amounts of analyte. They ae rapid and ‘an be automated, and they can be applied to smaller amounts of analyte when ‘combined with a sensitive instrumental technique for detecting the completion of the tttaion reaction, for example, pH measurement. Manual trations nowadys fre used in situations that require high accuracy for elatvely small numbers of “Samples, They are used, for example, to calibrate or validate more routine instu- fnental methods. Automated ttations are useful when lage numbers of samples must be processed, (A titration may be automated, for instance, by means of a colot Change or e pHl change thit activates a motor-driven buret to stop delivery: The ‘olume delivered may then be registered oa a digital counte—an example is given Ut the end of Chapter 14) In this section, the types of titrations that ean be per- formed are described andthe principles applicable to all types are given, includ ing the principles and requirements of a tiation and of standard solutions. The ‘Volumetric relationship described earlier inthis chapter may be used for ealculat~ Je quantative information about the tiated analyte. Calculations in volumetric tnalyes are given in Sections 5.5-5.7 incloding molarity and normality ter, nd ‘ackettrations, ‘TITRATION—WHAT ARE THE REQUIREMENTS? In a titration, the test substance (analyte) in a fash reacts with a reagent added from a buet as a solution of known concentration. This is refered to asa stan- dard solution, ands called the titrant. The volume of titrant required o just com- pletely react with te analyte is measured. Since we know the concentration as well ls the reaction between the analyte and the reagent, we can calculate the amount ‘Of analyte. The requirements of a tration are as follows: 11, The reaction must be stoichiometric. Thetis, there must be « well: NeC.H,0, + H,0 The seaction should be rapid. Most ionic reactions, as above, are very rapid, “These shouldbe no side reactions, and the resétion shouldbe specific. IE ‘there ae interfering substances, dese must be removed. Inthe above ex: !ample, there should be no other acids present.654 VOLUMETRIC ANALYSIS: HOW DO WE MAKE STOICHIOMETRIC CALCULATIONS? 159 44 Thete sold bea marked change in some property ofthe solution when the reaction is complete. This may be a change in color of te solution rin some electial or other physical property of the solution Inthe tation of act ai with sodium hydroxide, here sa mavked increase inthe pl ofthe solution when the reaction is complete. A color change {: unualybroogt boat by addon ofan inleator, whose color is de Teadent on the properties ofthe solution, fr example the pH “he pot at which an equivalent or stoichionetc amount of tant i ‘dedi called the equlvaleneepolnt. The point t which the reaction is |The egtence points te tee, ‘bserved wo be complete sealed the end pont, hati, when a change | ica end ofthe tiraon where the in some property ofthe solution is descted. The end point shoud oin- | nunbe of moles = nanbs of cide with the equivalence poit or beat reproducible interval from it | oles The end point ihe observed “The rection should be quantitative. That ie, the equilibrium ofthe xe- fe ttn, seton shouldbe fart he sgh 9 ata suiealy sharp change wil ‘crural te ed pont to obtain the desired accuracy. Ide euitium oes not ie fro the right then there wl be pada change inthe prop- ‘ety marking the end point (pH) and this wil be diieat to detect reiely ‘STANDARD SOLUTIONS—THERE ARE DIFFERENT KINDS A standard solution is prepare by disolving an accurately weighed quantity of a soluion standardized by trating highly pure material called a primary standard and diluting to an accurately a primary standard i saa second known volume in & volumetric Sask, Altematively if the material is not sufficiently ary sandr twill be less acute pur, a solution is prepared to give spproximately the desired concentration, and than a primary standard solton dor this is standardized by trating a weighed quantity of a primary standard. For tthe ees of tivations ‘example, sodium hydroxide is not sufficiently pure to prepare a standard solution iret. Tis therefore standardized by tating a primary standard eid, such as potassium acid phthalate (KHP). Potassium acid phthalate is solid that can be ‘weighed accurately. Standardization calculations are treated below. ‘A primary standard should fulfil these requirements: It should be 100.009 pure, although 0.01 to 0.424% impurity is vlerable it tis accurately known. 2, I should be stable 1 drying temperatures, and it should be stable indef- Iniely at room temperature. The primary standard s always dried before weighing? 3, I should be really available and fol inexpensive 4, Although not necessary, it should havea high formula weight Tis isso. | A high Formula weight means a that a relatively large amount of it will have tobe weighed o get enough | lurgor weight must be taken for a to irate. The relative error in weighing a greater amount of material wil. | given numberof moles. This reduces be smaller than that fora small amount. {he enor in weighing, 5, Iitis tobe used in titration it should possess the properties required for ‘atzaion sted above. In patcalar, the equilibrium ofthe rsetion should be far to the right so that a very sharp end point wil be obtained, Tie ew ete hon he ry tote i yeeSSTOICHIOMETRIC CALCULATIONS: THE WORKHORSE OF THE ANALYST CLASSIFICATION OF VOLUMETRIC MeTHODS— WHAT KINDS ARE THERE? “There are four general classes of volumetric or ttimetrc methods. 1. Acid-Base. Many compounds, both inorganic and organi, are either acids or ‘bases and can be titrated witha standard solution ofa strong bese ora song facid, The end points of these titration are easy to detect, either by means of fn indicator or by following the change in pH with a pHT meter. The aciity fnd basicity of many organic acids and bases can be enhanced by titrating in ‘nonaqueous solvent, The result is a shaper end point, and weaker acids fan bases ean be titrated in this manne, 2. Precipitation. ln the case of precipitation, the titrant forms an insoluble prod- uct with the analyte, An example isthe tration of chloride ion with silver nitrate solution to form silver chloride precipitate, Again indicators can be ‘sed to detect the end poiat, orth potential of the solution ean be monitored clectialy 3. Complexomeric, In complexometsc tations, the tant is a reagent that forms a water-soluble complex with the analyte, a metal jon. The titrant is ‘often a chelating agent.“ The reverse tiation may be caried out aso. Ethyl- tnediaminetetraacetc acid (EDTA) is one ofthe most useful chelating agents Used for titration, Ie will eact with a large numberof elements, and the re- factions can be controlled by adjustment of the pH. Indicators ean be used to form a highly colored complex with the metal ion. 4. Reduetion-Osidation. These “redox” tations involve the tteation of an ox- idixing agent witha reducing agent, or vice versa. An oxidizing agent gains tleetrons and a reducing agent loses eloctons in a reaction between them. ‘Thete must be a sufficiently large difference between the oxidizing and re- ducing capbilities ofthese agents forthe reaction to go ro completion sit ‘give sharp endpoint; that f, one shouldbe afairy strong oxidizing agent {Gtrong tendency to gin electrons and the other a fil strong reducing agent (strong tendeney to lose elettons). You can use appropriate indicators for these titrations, or you may employ various eletromezic means to detect the nd point. "These diferent types of titrations and the means of detecting ther end points will be treated separately in succeeding chapters. 55 Volumetric Calculations—Let's Use Nolarity ‘We shall use molarity throughout the majority ofthe text for volumetric ealcula- tions. However, another useful concentration unit for volumetric calculations is normality, which uses the concepts of equivalents and equivalent weights in place of moles and formula weighs. Normal concentration depends on the partic- blr reaction, and the reaction should be specified. Some instructors prefer. in- troduce te concept of normality, and students are likely to encounter it in reference books, Therefore, «review of equivalents and normality is given following te dis- cussion of esloulatios using molarity. “tng get eens ve on tek ofr oi ye ogg age at ‘Seti to or me pup pale of soplong wi stl EDTA bas ts Bop