NATIONAL UNIVERSITY CONANT * CHAPTER OBJECTIVES: - Explain the basic principles of volumetric, methods in analytical chemistry. - State the chemical basis of titrimetric analysis. - Construct and evaluate titration curves and their| applications in quantitative analysis. - Apply concept of acid-base chemistry in volumetric and titrimetric methods. - Perform analysis of systems involving neutralization titrations. ‘Twraton err Titration methods are based on determining the quantity of a reagent of known concentration that is required to react completely with the analyte. The reagent may be a standard solution of a chemical or an electric current of known magnitude. + In volumetric titrations, the volume of a standard reagent is the measured quantity. + In gravimetric titrations, the mass of the reagent is measured instead of its volume. + Incoulometric titrations, the quantity of charge required to complete a reaction with the analyte is the measured quantity. + In redox titrations, volumetric methods are used in which the analytical reactions involve electron transfer. Additional titration methods include amperometric | titrations and spectrophotometric titrations. + A standard solution (or a standard titrant) is a reagent of known concentration. - In a titration, a standard solution is slowly added from a buret or other liquid-dispensing device to a solution of the analyte until the reaction between the two is judged to be completed. - The volume or mass of reagent needed to complete the titration is determined from the difference between the initial and final readings. + Back-titration is a process in which the excess of a standard solution used to consume an analyte is determined by titration with a second standard solution. - Back-titrations are often required when the reaction rate is slow or when the standard solution lacks stability + The equivalence point is the point in a ti when the amount of added standard reagent is equivalent to the amount of analyte. + The end point is the point in a titration when a physical change occurs that is associated with the condition of chemical equivalence. « Indicators produce an observable physical change at or near the equivalence point. + A_TYPICAL TITRATION " ES PROCESS SET-UR s = + The appearance of the a a apparatus during titration / and the titration end i |)/ °* =? point. A primary standard is a highly purified compound that serves as a reference material and requires the following: high purity "atmospheric stability . absence of hydrate water (anhydrous) }. modest cost . reasonable solubility in the titration medium . reasonably large molar mass Og aeNe Because very few compounds approach the criteria to be a primary standard, less-pure secondary standards are often used. A secondary standard is a compound whose purity has been determined by chemical analysis. will 1. be sufficiently stable 2. react rapidly with the analyte 3. react more or less completely with the analyte 4, undergo a selective reaction with the analyte that can be described by a balanced equation Two methods are used to establish the concentrations of standard solutions. "In the direct method, a carefully determined mass of a primary standard is dissolved in a suitable solvent and diluted to a known volume in a volumetric flask. * In standardization, the concentration of a volumetric solution is determined by titrating measured quantity of a primary or secondary standard or an exactly known volume of another standard solution. it against. a carefullyNATIONAL UNIVERSITY In standardization, the titrant to be standardized is used to titrate one of three options: 1. a known mass of a primary standard 2. a known mass of a secondary standard 3. a measured volume of another standard solution A titrant that is standardized is sometimes called a secondary-standard solution. + When possible, the direct method is preferable to standardization because the concentration of a secondary-standard solution is subject to larger uncertainty than is the concentration of a primary- standard solution. The concentration for the standard solutions used in most titrations is generally expressed as either molar concentration, ¢, or _~—normal concentration, CN Molar concentration - the number of moles of reagent in 1 liter of solution. Normal concentration - the number of equivalents of reagent in 1 liter of solution. Most volumetric calculations are based on two pairs of equations. + For chemical specie A, the first pair Equation 11-1 and Equation 11-2 The second pair is Equation 11-3 and Equation11-4, where V is the volume of the solution montana = vO) x8 eet soma = vt x (2084) (44 Molar concentrations of standard solutions can be calculated in several ways. + The number of moles of a compound can be calculated by multiplying the volume of the solution in liters by the concentration of the compound in moles per liter and then using this information to calculate the mass of the substance by rearranging Equation 11-2 (see Example 11-1, next). + Example 11-2 shows a similar calculation for Na,CO, a species that dissociates to produce two Na+ ions in solution, in which unit conversions are required. EXAMPLE 11-7 Describe the preparation of 2.000 L of 0.0500 M AgNO, (169.87g/mol) from the primary-standard- grade solid. Soluion aunt MNO, = Yai) * Egat) = 2001 » 2080, «6 so ms Aato, To.btain he mass of AgNO, rearrange Equation 11.2 0 give 1887 9490, ima, = art00matagnas « 8 Aa ‘halo sen shou br pe dtahig 1638 gol AN, ese coane tes eonaen mesons EXAMPLE 11-2: A standard 0.0100 M solution of is required to calibrate an ion-selective electrode method to determine sodium. Describe how 500 mL of this solution can be prepared from primary-standard Na,CO, (105.99 g/mol) Sotiion ‘Sncantaton of 06100 nts saa, se mci nce fe vue ain miter. Because Na,CO, dissociates to Give wo Na on, the numberof lines of Na,CO, needed rent Na,CO, = 500m = From the definition of mitimote. ase ee 105.90 9N8,CO,_ Na,C0, = 250mmNescO; » 10590 ONC 35 mg NaCO, ‘Since thre are 1000 mig or 0.001 gma, the soluton should be prepared by dissolving 0.285 9 o w,co, in water and cut to 500 mL Examples 11-4 and 11-5 show how to determine the concentration of a solution that has been standardized against a primary standard or another standard solution. + Example 11-5 shows how to calculate the amount of analyte in a sample from titration data. Both types of calculation are based on three algebraic relationships: Equations 11-2 and 11-4 and the stoichiometric ratio of the number of milimoles of the analyte to the number of millimoles of titrant EXAMPLE 11-4: ‘ 50.00-mL portion of an HCL solution required 29.71 mL of 0.01963 M Ba(OH), to reach an endpoint with bromocresol green _ indicator. Calculate the molar concentration of the HCl. Solution Inthe tation, 1 mmol of Ba(OH), reacts with 2 mmol of HCt Ba(OH), + 2HCI-» BaCl, + 24,0 “Thus, the stoichiometric aioe aio = _2 MOLHCL stletiomatie rato * Frnt Ba OF),NATIONAL UNIVERSITY “The nue of maiotes thw standard calculated by substtting a Eaton 1-8 mount (0H), = 20.71 myBa(on, = cores MAEAOM), or, Eaton, Bao ‘af rtf tines ot Hl mts esd te stchoneic Tesooort ‘To obtain the numberof milimoles of HCI per mL, divide by the volume ofthe acid. Therefore, = (28.710.01963%2)mmolHCL oo '50.0mLHCL e mmolHCu—> 5pszaur] =o.023328 MOC =9 o2339M EXAMPLE 11- ‘A 0.8040-g sample of an iron ore is dissolved in acid. The iron is then reduced Fe* and titrated with 47.22 mL of 0.02242 M KMnO, solution. Calculate the results of this analysis in terms of (a) % Fe (55.847 gimol) and (b) % Fe,O, (231.54 g/mol) lon QwAlys mas at Sot FRE ak vo Ey ce 002240 Me creep) FRc es ot we a ae sees AE sonar ‘hereon ft rte we ego by he sain ‘The mass of Fis then given by masa Fe = (4722 x 0.02242 » §)mmetF@™ x oosseer OF (ar x 0 5) met 005586 The % Fete (4722 0.92242 « 5 x 0.05568 Fe = secant x 100% = 967% ') To detrmine the coect stoichiometric rato, note that SF = MoO Therefore, 5 FeOym 15 Fe* = 3 MAO” ona Smet mentors ene + $8 sta, = (ono mats ven SB nn seman, EON CURVES The most widely used signals to detect an end point are + changes in color due to the reagent (titrant), the analyte, or an indicator. + a change in potential of an electrode that responds to the titrant concentration or the analyte concentration, Titration curves are plots of a concentration- related variable versus titrant volume. In a sigmoidal curve, the p-function of analyte (or sometimes the titrant) is plotted as a function of titrant volume as shown in Figure 11-2a, = In a linear segment curve, measurements aré made on both sides of, but way away from, the| equivalence point. The vertical axis represents an instrument reading that is directly proportional to the concentration of the analyte or the titrant as shown in Figure 11-2b + Advantages of sigmoidal curves are speed and ‘convenience. + Linear segment curves are advantageous for reactions that are complete only in the presence of a considerable excess of the reagent or an analyte. Table 11-1 illustrates the major changes in the relative concentrations of reagent and analyte that characterize the equivalence point in a titration. Solo tae oo» Figure 11-3 illustrates the large changes in relative equivalence that occur in the region of chemical equivalence using data from the fourth and fifth oma” columns of Table 11-1NATIONAL UNIVERSITY FIGURE 11-3: Feature 11-3: Calculating the NaOH volume Shown in the First Column of Table 11-1 (1 of 3) Pr othe eaiece pr 0") es he conceneaton of wea lig.) The concanaton of HC! eal the ona runtar of mimces of ¥HG1{.od me 0 000M rans the numbe fries oF NaOH oaee8 (cu H0.1000 1) ded by he tal voume eine SOKRON: ai) = dual n= [hor] = 2 ag 0 EN Wm Van esha 1IOHENAOH ae Teuton ste Gifs moh = oo! S000] + eto") = so iro Let Cotecing he ems containg a, ves M%o,(0.100 + [H,0"]) = 5.000 ~ s000[H.0"] ‘5000 ~ 50.00{H.0" Moen * G7000 + [HO ‘Thusto edie (o")-o010 MS Yoo « aon s00100 Im “chalenge: Use he sare reasoning show a beyond equatece pi s.000f0r'] + 5.000 Moor * “000 ~ [Ow abet! oliye? = awe) +? OfNATIONAL UNIVERSITY BGP RL Uae ea TT PRINCIPLES OF NEUTRALIZATION TITRATIONS Important Equations: Indicator pH range pk, pKst pH+pOH. |4 STANDARD SOLUTIONS + The standard solutions used in neutralization titrations are strong acids or strong bases as these react more completely with an analyte than do weak acids and bases and therefore produce sharper end points. + Standard solutions of acids are prepared by diluting concentrated hydrochloric, perchloric, or sulfuric acid. + Nitric acid is seldom used. + Standard solutions of bases are usually prepared from solid sodium, potassium, and occasionally barium hydroxides. ACID- BASE INDICATORS ‘An acid-base indicator is a weak organic acid or @ weak organic base whose undissociated form differs in color from its conjugate base or its conjugate acid form. + Figure 12-1 shows examples of the colors and transition ranges of 12 common indicators. Mm ini wi itil i UNTTTIITNL ‘i iii NTT Equation 12-1 is the _equilbrium-constant expression for the dissociation of an acid-type indicator. [Hon] 8 ln} (124) [Equation 12-1 can Tatin) any | be rearranged to [HO'J=Ki,n) (2) give Equation 12-2. u + Equation 12-3 is derived from the negative logarithms of | the expressions for the pH of acid color and the pH of basic color. indicator pH range=pk,+1 (12-3) Figure 12-3 shows indicator pH as a function of pH (px, =5.0) There are two types of error in acid-base 'titrations. « Determinate error occurs when the pH at which the indicator changes color differs from the pH of the equivalence point. This type of error can be minimized by choosing the indicator carefully or by making a blank correction. « Indeterminate error originates from the limited ability of the human eye to distinguish reproducibly the intermediate color of the indicator. Variables that influence the behavior of indicators include the following: - Temperature. - Ionic strength of the medium, - The presence of organic solvents and colloidal particles. Table 12-1 shows common aci and their properties. ‘base indicators Ege orc pte bie TITRATION OF STRONG ACID AND BASES The hydronium ions in an aqueous solution of a strong acid have two sources: * the reaction of the acid with water = the dissociation of water itself An applies for a solution of strong base.NATIONAL UNIVERSITY rans) TITRATING A STRONG ACID WITH A STRONG BASE It is important to distinguish between calculated hypothetical titration curves and experimental titration curves observed in the laboratory. + Three types of calculations must be done to construct the hypothetical curve for titrating a solution of a strong acid with a strong base and these types correspond to the stages of titration: 1. preequivalence 2. equivalence 3. postequivalence + In the preequivalence stage, compute the concentration of acid from its _ starting concentration and the amount of base added. + At the equivalence point, the hydronium and hydroxide ions are present in equal concentrations and the hydronium ion concentration can be calculated direction from the ion-product constant for water, K,. Che) - Cow ky + In the post-equivalence ‘stage, me anayytical concentration of the excess base is computed, and the hydroxide ion concentration is assumed to be equal to or a multiple of the analytical concentration The relationship between the _ion-product concentration for water, pH, and hydroxide concentration is illustrated in the equation below. pK, =pH+pOH Example 12-1 Generate the hypothetical titration curve for the titration of 50.00 mL of 0.0500 M HC! with 0.1000 MNaQH at 25°C. wanatvoin—CH9°] » Tate! (noi fe ofore any base i added, te Soksion it 0.0500 M in 1,0" and AVC LO"]= 19 0.0800 =1.30, ‘Atter Adaition 10.00 mt of Reagent wl Pacis wl ‘Te hyena ations a a result reaction win bth tho base and aon 3 800. Serig yn Gus smmolHCtremaining ater ation ot NaOH ‘walvohme sn _ tial mmolHCi-nomma!NaQH adsed ‘otal volime soln 00 ml x 005004) (10.00 0.10008) 30.00mL* 000m (2500mmot-1.00mmes) ‘0.007mL (Ho"]=250%10°M PH =-log[H0"]=-109(2'50 10") =1.602 «1.60 a ongial pret! 2.50%10°M Changes in pH During the Titration of a Strong Acid with a Strong Base Cliw') = Low) po fe 2 bios 09 71 14. ptayoe After Addition of 25.10 mL of Reagent Vv The ettonnow comme mero MOH and eee we Cees oH (4 90 ‘The equitiam cencertaton of hyo on [or ]neanet 39-10" orjesneyam | 1h) |) ‘Asvonalvales beyond te equivalence pot are calculated n the sare way ‘Therenuts ofthese Computations oe show teas ee ows O Tale 122. )4- 388