PUT RT TES Covers all course fundamentals and supplements any class text 590 fully worked problems > Hundreds more practice problems Ideal for independent study Schaum’s Outlines help you get better grades Use with these courses: ( Physical Analytic Chemistry Laboratory ( Intensive General ChemistryRESEAPOY HRRARY 4..J. RESEARCH: *TCuBNISTRY intematonst Car Sciences UNIVERSITY OF KARACHI Accession No.: J + 34 . Call Nos Volume: pate: 20-05-2004, _SCHAUM'S OUTLINE OF THEORY AND PROBLEMS of ANALYTICAL CHEMISTRY ADON A. GORDUS, Ph.D. Professor of Chemistry University of Michigan SCHAUM’S OUTLINE SERIES McGRAW-HILL New York San Francisco Washington, D.C. Auckland Bogoté Caracas Lisbon London Madrid Mexico City Milan Montreal New Dehli San Juan Singapore Sydney Tokyo Toronto\DON A. GORDUS received a B.S. in Chemistry in 1952 from the inois Institute of Technology and a Ph.D. in 1956 from The University in. He then joined the staff of The University of Michigan is Professor of Chemistry. He was a Guggenheim Fellow in as the Phi Lambda Upsilon Outstanding Teacher. He has cover 70 research articles concerned with energy transfer pro- | and historical artifacts, as well as of clinical, environmental, stic samples. ‘of Theory and Problems of ‘CHEMISTRY ‘by The McGraw-Hill Companies Inc All rights reserved. Printed in the Except as permitted under the Copyright Act of 1976, no part of be reproduced or distributed in any form or by any means, or stored erieval system, without the prior written permission of the publisher David Beckwith Marthe Grice nager. Nick Monti | Cataloging in Publication Data ne of analytical chemistry. iic—Quamtitative. 1. Tile,Preface This Outline, which began as a study guide for students in quantitative analysis courses taught by the author, contains a number of original approaches introduced in these courses. They include the criteria for using various simplified ‘equations in calculating the pH of weak-acid solutions and the solubilities of precipitates (including a rule for neglecting the water equilibrium), the use of a lever analogy in identifying principal species in polyprotic acid mixtures, the use of two different symbols to differentiate between half-cell and full-cell potentials, and a simple procedure for converting an equation based on ideal solutions to one in which non-ideal activity coefficients are needed. Numerous problems are concerned with non-ideal solutions. The precision of measurements and the resultant significant figures are emphasized throughout the Outline, and formulas for the propagation of errors are derived and applied. Although instrumental analysis is outside the scope of this book, introductory material is presented in Chapters 12 and 13 on phase equilibria, chromatography, and spectra. The last chapter treats the analytical uses of radioactivity, an important topic often ‘omitted from standard texts and courses While directed primarily toward students of Analytical Chemistry, this Out- line should also be of value in the more advanced (honors) introductory chemistry courses that include more rigorous treatments of ionic equilibrium, It was the author's many students who defined the scope and depth of coverage of this Outline. Through their excellent questions, these students constantly helped to clarify the approaches used in the course: they were the real teachers. Several students directly assisted in the preparation and reading of the text, and the editor, David Beckwith of McGraw-Hill, gave final shape to the Outline. ‘The author is grateful t0 them all ADON GorpusContents Chapter, 1 ANALYTICAL AND MATHEMATICAL REVIEW L 1 1 1 1 1 1 1 Units, Constants, Coneentrations 2 Balaneing Redox Equations 3 Stoichiometry olving Equations 5 Pocket Calculators ificant Figures 7 Implicit Assumptions Chapter 2 STATISTICS AND PROBABILITIES, 2.1 Accuracy and Precision 2.2 Systematic and Random Errors 2.3 Statistical Symbols and Definitions 2.4 The Gaussian (N—>) Distribution 2,5 Student's 1 (N Finite) Distribution 2.6 Tests for Significance 2.7 Propagation of Error 2.8 Rejection of Data x 2.9 Linear Least-Squares Data Fit x0 Chapter 3| FREE ENERGY AND CHEMICAL EQUILIBRIUM 16 3.1 Gibbs Free Energy 46 3.2 Activites 47 3.3 Chemical Equilibrium; Equilibrium Constants 4” 3.4 Principle of Le Chater si Chapter 4 STRONG ACIDS-STRONG BASES. « 4.1 The Water Equilibrium w 42 Caleulation of pH ‘i 43 Titration Equivalence Point. 8 4.4 Principal Species 4 Chapter 5 SIMPLE WEAK ACIDS AND WEAK BASES 2 5.1 Equilibrium Constants 3 5.2 Caleulation of pH 4CONTENTS Chapter 6 WEAK ACID OR WEAK BASE TITRATIONS 86 6.1 Introduction 86 6.2 General Equation for Titration Curves 86 6.3 Titration Regions 7 6.4 Concentration Shifts to Equilibrium Po 6.5 Simplified Equations for the Titration of a Weak Acid 90 6.6 pl Color Indicators o4 Chapter 7 POLYPROTIC WEAK ACIDS... 2. 6. . - 104 7.1 General Properties 104 2 pH Approximations 07 7.3 General pH Equation 109 7.4 Identification of Principal Species 109 7.5 Solutions of Known pH m Chapter 8 PRECIPITATES AND SOLUBILITIES . . . 127 8.1 Solubility Product 127 8.2 Solubility of Salts 127 8.3 Precipitation Titrations 18 8.4 Classification of Precipitates BI Chapter. 9 COMPLEX ION EQUILIBRIA... . . 9.1 Introduction 9.2 Common-on Effect 9.3 Complexation Chapter 10 ELECTROCHEMICAL CELLS... 6... 166 10.1 Galvanie Cells 166 10.2 Cell Thermodynamics 166 10.3 Combination of Half-Cell Reactions 167 10.4 Cell Notation 168, 10.9 The S.C.E. Cell 169 Chapter 1] POTENTIOMETRIC TITRATIONS... . . 179 11.1 Titration of a Single Ton 179 11.2 Titration of Mixtures 180 11.3 Redox Titration Indicators 18CONTENTS Chapter 12 PHASE SEPARATIONS AND CHROMATOGRAPHY. . . . . . . . 197 121 Introduction . 7 12.2 Fractional Distillation : 197 12.3 Solvent Extrations : 198 124 Chromatographie Separations 199 Chapter 13 SPECTRAL MEASUREMENTS © 2. 2). ee ee .. m3 13.1 Unis of Measurement 23 132 Beer's Law : 214 13.3 Photometric Taraions 216 Chapter 14. RADIOACTIVITY... . sat Rents en oe cos 14:1 Types of Decay 2 142 Deway Rate Equations Ll a6 143 Neutvon Activation ns 14.4 Radioactivity Stat 28 APFENDIR-A rap eee ate toe) «8 DOSER perches ele eg cg ote ooh 0)Chapter 1 Analytical and Mathematical Review 1.1 UNITS, CONSTANTS, CONCENTRATIONS Analytical chemistry by and large employs the International System of Units (SD) if itis agreed that the gram (used for masses) and the liter (used for fluid volumes) are to be taken as SI derived units, Table 1-1 collects important SI and non-SI units, with the latter marked by an asterisk. By definition, the SI mole is that amount of matter which consists of as many elementary units as are present in 0.012 kg of pure "C; it thus is identical with the traditional “gram mole.” Remember that while the Kelvin and Celsius temperature scales employ the same degree, the zero of the Celsius scale is located at +273.15 K. Decimal fractions and multiples of the SI units, as well as of the cal and eV, may be indicated by the prefixes given in Table 1-2. Thus, for instance, 1am’ Latm = 101.325 kPa 1 ‘Table 1-1 Physical Quantity Unit Name Unit Symbol Definition Amount of mole mol Substance Density, kilogram per gin? Concentration cubic meter ram per liter wk 1 g/L=1 kgim* Blectrie Charge coulomb ¢ 1C=1 Ass Electric ampere A Current Electric volt v 1V=1WA Potential =15C Energy J LJ=1Nem cal 1 cal = 4.184 3 (exactly) electron volt ev TeV = 1.6022 10-3 Force newton, N LN= 1 kg-mss? Frequency hertz Hz VH=1s" Length meter | m centimeter em Lem= 107m angstrom* A 10m inch” in 2.54.em (exactly)2 ANALYTICAL AND MATHEMATICAL REVIEW [CHAP. 1 Table 1-1 (cont) Physical Quantity Unit Name Unit Symbol Mass Kilogram |g ram 5 1 p= 10 ks pound mass? bm 1 bm = 453.6 g atomic mass unit” u 1 w= 1.6606 10” kg Power watt w 1W= 15/8 Pressure pascal Pa 1Pa=1 Nim atmosphere* atm 1 atm = 101 325 Pa (exactly) torriceli torr 760 torr= 1 atm Radioactivity beequerel By 1 Bg= 1 decay/s Curie* G 1Gi=3.7%10" Bq “Temperature kelvin K degree Celsius c ‘Time second : Volume cubic meter a cubie centimeter om lier L re [Fein [Pete | Symbat | marine | Pein | Smiel to" deci da 10" deka da 10? conti c 1 hecto, h 10> milli m w kilo. k 10° micro: » 10° mega M are | fees | ce’ 1am, |e 10°? pico Pp 10% tera T Physical constants needed in analytical chemistry are listed in Table 1-3. The spectral energy factor will be of use in Chapter 13. Table 1-4 gives the terms commonly used to state the concentration of a solution. In this book, molarity will be employed almost exclusively, and the symbol M will also be used as an abbreviation for the physical unit mol/L. It should be remembered that the molarity of a solution will vary (decrease) as its temperature increases, whereas molality is temperature independent. The two measures are related by the equation 100M eam (11) in which p is the (temperature-dependent) density (in kg/m’) of the solution and W is the molecularCHAP. 1) ANALYTICAL AND MATHEMATICAL REVIEW 3 weight (in g/mol) of the solute. The normality of a solution depends on the reaction. For a solution that will be used in a redox reaction molecular weight equivalent weight = —————TOISCU Welk _ absolute change 1 in oxidation state For a nonredox reaction, the denominator is replaced by “number n of replaceable hydrogens, hydroxides, or their equivalent.” In either case, m is reaction dependent, Normality and molarity are related via N=nM (2) In any redox reaction at the equivalence point, the product of normality and volume—i.e., the number of equivalents—must be the same for the substance being oxidized and the substance being reduced. Using (1.2), this condition takes the form ngMV, — nM,V, (3) ‘Table 13 (022% 10* molecules: mol * 16.487 KC mol = 23.061 keal V"'= mol! Gas constant R= 8314 1K t-molt 987 eal K-mol! 2.05 em’ +atm+K-*+mol* = 0.08205 L+atm>K-!+ mol! Avogadro constant Na Faraday constant # Electronic charge magnitude ¢ = 1.6022 10" C Planck constant = 6.6262 10 Js Speed of light c= 2.998% 1 mes? Spectral energy factor fae = 1239.8 nm-eV eV /8066 em’ ‘Table 1-4 Term Definition molarity (M)= moles solute/liter solution molality (wt) = moles solute/kg solvent normality (N)= equivalents solute/iter solution formality (F)= formula weights solute/liter solution mole fraction (x)= moles solute/(moles solute + moles solvent) wt% = (gsolute/g solution)(100%) ppm by wt = jgsolute/g solution ppb by wt ng solutelg solution meq/lter meq solute/liter solution mg% = mg solute/100 mL solution Included in Table 1-4 are three terms used in clinical analysis. The first, wt%, is usually associated with the analysis of tissue samples, and is often qualified to indicate if it is based on a wet, dry, or ashed sample. The second, meqiliter, occurs in the analysis of ionic constituents in body fluids, such as Mg” in blood. The third, mg %, has a name that does not seem to fit its definition Fortunately, this ambiguous term has fairly limited use in clinical analysis.4 ANALYTICAL AND MATHEMATICAL REVIEW [cHaP. 1 1.2 BALANCING REDOX EQUATIONS STEP 1. Determine the oxidation states in both the reactant and product species for the element that undergoes oxidation and for the element that undergoes reduction. Fractional oxidation states are occasionally found, although they usually are a mixture of integer states. Assume values of oxidation states in the following sequence: (i) hydrogen is +1 ‘except in H., where it is zero; (ii) oxygen is ~2 except in peroxide, where it is ~1, or in O,, where it is zero. For organic compounds, recommended procedure is to assign H= +1, followed by O= ~2, halogen = -1, and to calculate the oxidation state of carbon, if it is the remaining element, by difference. If the organic compound also contains nitrogen, then assign C= +4, and calculate the oxidation state of nitrogen by difference STEP 2. Calculate the total increase in oxidation state for the reactant jon or molecule that contains the element being oxidized, taking into account the number of atoms of the oxidized element per reactant ion or molecule, Similarly, calculate the total decrease in oxidation state for the reactant ion or molecule that contains the element being reduced. Balance these reactants by assigning them coefficients which make the two totals equal. STEP 3. Many reactions require extra hydrogen- and/or oxygen-containing species to complete the balancing. If the reaction takes place in an acidic solution, then H and/or H,O may be added to the reactants and products as needed. If the reaction takes place in a basic solution, OH” and/or H,O may be added as needed. Of the three quantities H, O, and charge, at most two will be needed to complete the balancing, Select first that quantity which allows an unambiguous calculation. Thus, if the solution is acidic, the equation should not be first balanced in terms of hydrogen, since one cannot decide whether to add it as H’ or as H,O. Here, charge or oxygen balance is unambiguous; the former relies only on the addition of H’, the latter only on the addition of H,O. Ii the solution is basic, charge balance should be performed first, since it relics only on the addition of OH, whereas hydrogen or oxygen balance could use either OH” or HO. Following the charge balance, either O or H balance can be performed using HO, EXAMPLE 1.1 Complete and balance the redox reaction where CIOs~ reacts with HNO> in an acidic solution to produce Cla(g) and NOx ‘The chlorine is +5 in CIOs and zero in Clo(g), so that the reduction is ~S/CI= —S/CIOy-. The nitrogen is +3 in HNO; and +5 in NOs, so that the oxidation is +2/N=+2/HNO;, Therefore, balancing of the total ‘oxidation and reduction changes requires that CIOs react with SHNOs, and the partially balanced equation is: 2ClOs + SHNO}> Clg) + 5NOx The remaining balancing will be on charge and oxygen. The charge on the left is ~2, whereas it is -$ on the right; therefore, 3H” must be added to the right. There are a total of 16 oxygen atoms on the left, but only 15 on the right; hence, one HO molecule must be added to the right. The completely balanced equation is 2C10x" + SHNO2> Cla(g) + SNOs" + 3H" + HO ‘The fact that the hydrogen atoms also balance serves as a check. 13 STOICHIOMETRY Acid-base titrations are characterized by simple stoichiometry. If the reaction involves neu- tralization of a single hydrogen, HX + MOH H,0 + MX then mmols MOH = mmols HX. If the acid is diprotic and both hydrogens are neutralized, HY + 2MOH + 2H,0+ M,Y then mmols MOH = 2(mmols HY). If the acid is triprotie and all three hydrogens are neutralized,CHAP. 1] ANALYTICAL AND MATHEMATICAL REVIEW s H,Z+3MOH~3H,0 + M,Z then mmols MOH = 3(mmols H,Z). The mmol relationships may be converted into volume relation- ships through the definition of molarity: “mols _ mmols Vit) VimL) Other common stoichiometric relationships are based on oxidation-reduction processes. or mmols= M- V(mL) EXAMPLE 1.2. The permanganate oxidation of ferrous ion proceeds in an acidic solution according to the reaction MnO," + 5Fe* + SH" + Mn®* + SFe™* +4H,0 How many mL of 0.0240 M MnO. is required to oxidize 20.00 mL of 0.112 M Fe? ‘The stoichiometry requires that ‘mmols Fe** = S(mmols MnO.) (MV) = SMV) roe (0.112)(20.00) = 5(0.0240) V=187 mL. Ifa series of chemical reactions are performed to obtain a final product which serves as the basis for the analysis, it is necessary to determine, in addition, the stoichiometric relationship from one reaction to the next. EXAMPLE 1.3 A.0.250 g sample of « low-grade chromium ore was fused with sodium peroxide to convert the chromium to CrOs-. The sample was then dissolved in water, boiled, acidified (the CrO.- being converted to Cr07*), and titrated with 26.28 mL of Fe" solution. The products of the redox reaction were Fe'* and Cr". In 4 separate standardization titration, 46.48 mL. of the Fe" was required to reduce 0.1172 g of KxCriO, standard. ‘What is the wt % of Cr in the ore? What is the content in ppm by wt? “The balanced redox reaction is CHOP + 6Fe® + 4H" 2CP* + 6Fe™ + THO Since the molecular weight of KzCrOy is 294.19, the stoichiometry requires for the standardization: mmols Fe** = 6(mmols C07") 72m sM(4oa8 mt) o 11728) 253.9 mymal M0088 that is to say, the Fe* is 0.05143 M, The data for the analysis of the ore result (0.05143)(26.28) mmol Fe* = 6(mmols Cr0?-) so that there was 0.2253 mmol Crs0,?>. Since there are two Cr per Crx07", and since the atomic weight of Cris 51.996, we have: (0.2253 mmol Crs0;?"_2(51.996) mg Cr 100% = 9.37 wt % Cr 1 ‘mmol COF 250 mg sample (or 9.37 10* ppm Cr by wt. 1.4 SOLVING EQUATIONS ‘The availability of small programmable calculators makes it possible to solve even fairly complicated equations of the sort that can arise from multiple equilibria systems. However, even in these cases, simplifications are sometimes useful.6 ANALYTICAL AND MATHEMATICAL REVIEW [cHAP. 1 Quadratic Equation If an equation can be reduced to a quadratic, ax?+ bx +¢=0, then: -b+ VB 4ac x oo (A) ‘Successive Approximations Especially for higher-order equations, successive approximations can be the most direct ap- proach. A starting value for the unknown, x, is used in one of the x-terms, and the value of x is calculated on the basis of the remaining term or terms. This value becomes the new starting value, the calculation is repeated, ..., until a stable value is attained. EXAMPLE 1.4 An equation for the hydrogen ion concentration, x, of a solution is: 2+ 0.0350 - 0.116 = 0 Find x. First get an approximation for x by neglecting one ofthe x-terms in the equation (.e, use the starting value 4400 in that term). For instance, ifthe xterm is neglected, then a first approximation for x is _ 0.6 | “00350 For the second approximation, substitute xy in the x°-term and recalculate x 0.116 3.2314 fe at ‘The third approximation is 19x10" It is clear by now that this set of successive approximations will lead nowhere. Therefore, let us instead start by neglecting the 0.0350.x-term; this results in as the firs approximation. The second approximation is [0.116 (.0350)(0.488)) ” 0.463 ‘The third approximation is x5 = [0.116 — (.0350)(0.463))"" = 0.464 which is within 1% of x2. Thus, we can stop here, and write x~0.464, Graphical Intersection Method ‘On occasion, an approximate solution to a complicated equation is known. Let the equation be written in the form A(x) = B(x). Values of each of A and B are calculated for two or more values of x in the immediate vicinity of the approximate solution. These values will plot as two straight lines (very nearly), whose point of intersection yields the solution x. EXAMPLE 1.5. The theory of Chapter 3 gives for the solubility, S, of TICI(s) the equation Loa 2log $+3,699 = UNS Le 0984V3 A(S) BGS)CHAP. 1] ANALYTICAL AND MATHEMATICAL REVIEW 1 An approximate value of S, S)= 1.40% 10%, can be obtained from the solubility product for TICI on the assumption that the solution is ideal. We compute the following values of A and B: A B 149«10 | ~0.0087 | 40.1085 soxio? | 400812 | 40.119 oxi? | +0205 | 401214 Se s Ss ‘S; wasarbitrarily chosen as being within 10% of Ss. The fact that the corresponding A- and B-valuesare closer ‘together than the values at S, but with the B-value still exceeding the A-value, shows that the desired solution must be larger than Sy. At Sz, however, the A-value isthe greater; hence, he solution must lie between S; and S>. Figure [1 shows the linear graphs and their intersection at $= 1.62% 10 8-8, at $= 1.107 AGS) oF BIS) 15 POCKET CALCULATORS A number of features of pocket calculators are especially useful in calculations for analytical chemistry Fractional Roots The y" function on a calculator can be used to calculate fractional roots. For example, 3.65" = 3.65", Therefore, keying in y = 3.65 and x = 0.333, followed by pressing the y* button, will yield the cube root of 3.65, which is 1.54, pH and pOH Calculations It, for example, you are given [OH'] = 2.76 10°, simply key in that number and the logy bution will yield POH = ~3.559. Now, pH = 14.000 ~pOH, and ~pOH is already displayed; so all that remains is to add 14,000 to that value, obtaining pH = 10.441. [As indicated in Section 1.6, be certain that the number of decimal places in the pX value is equal to the number of digits in X.]8 ANALYTICAL AND MATHEMATICAL REVIEW [cnap. 1 Range and Capacity Most calculators have a maximum range of 10° to 10°. On those few occasions where calculations could exceed the range, carry the exponents in a separate calculation You should make use of the full calculator capacity (usually 8 to 10 digits) in all intermediate calculations. [Most calculators do this automatically, even though fewer digits might be displayed.) Round off the final value in accord with the rules for significant figures (Section 1.6) Linear Regression Many calculators have built-in programs for standard deviations and linear regression. Deter- mine, for your calculator, how the values ¥x, ¥y, ¥x7, Yy*, and Exy are stored, since these summations can be useful in other statistical calculations described in Chapter 2. 1.6 SIGNIFICANT FIGURES The rules that follow, while standard, must be used with the caution that the actual uncertainty in 4 final value will always be greater than that given by these rules. RULE 1. Values are reported so that they contain all digits known with certainty, plus a digit that is known only to within #1. If an actual uncertainty is calculated, for example, as a standard deviation, then the standard deviation automatically determines the number of significant figures. It is often useful to know the value of the standard deviation to two digits, and this requires that a second uncertain digit be shown in the original value. EXAMPLE 1.6 A repeated series of measurements results in an average of 3.267 and a standard deviation of 0.038. This can be written as 3.267 + 0.038, since it is clear from the value of the +-term that only the first two digits in the average value are certain. In such cases, the second uncertain digit is frequently displayed as a subscript: 3.267 0.03. If only one digit of the standard deviation was to be kept, the rules of rounding would be applied and the result would be written as 3.27 = 0.04, RULE 2. Zeros between nonzero digits are always significant. Leading zeros (as in 0.0081) merely locate the decimal point; they are never significant. Trailing zeros of integers may or may not be significant. EXAMPLE 1.7. To indicate that a quantity notated as 30000 has four significant figures, some authors would write 30000. The best practice in the case of trailing zeros—or in general to show which figures are significant—is to use scientiie notation: 81109 3,000 108 RULE 3. In the addition and/or subtraction of a set of values, the number of significant figures in the result is governed by the least certain value. For instane 10.628 + 1.2-+ 376.7 + 0.0039 = 388.5, since neither 1.2 nor 376.7 has digits past the first decimal place. RULE 4. In multiplying and/or dividing a set of values, the number of significant figures in the final Value may not exceed the number of significant figures in the least precise multiplier or divisor. Thus, 28/087) __ |, (©.0373)6298.3) because the least precise value, 2.8, has only two digits. EXAMPLE 1.8 An improvement on Rule 4 may be derived from the theory of Chapter 2 [sec (2.9)], whereby the ‘number of digits in the final value is determined by the fractional uncertainties in the multipliers or divisors. To see how this works, consider the evaluation ofCHAP. 1] ANALYTICAL AND MATHEMATICAL REVIEW 9 (©8079) ,__(103)679) (2305)(1.624) ~ (1305)(1.628) based on (a) Rule 4, (b) the improvement (a) X-=18 (because 98 has only two digits) and ¥ = 184 (because 103 has only three di (0). Since the fractional uncertainties 8) the least significant values (98 and 103) are the same: 0.010 = 1.0% = 1 part in 100 ke Sule fA SRE ad Sula trex us AG tan RR Yt wuts ma vs RULES, IF Om Kv where WWE an aay ie uel Reem emmareae ek ao_ ax o ie i.e., the fractional uncertainty in Q is equal to the fractional uncertainty in x multiplied by the exponent a. EXAMPLE 1.9 If Q = ((.0878)'* = 0.95251 and if Ax = 0,001, then 40-00. ssasi(z)( and five digits are proper for Q. But if = (0.0878) = 7.4112 10, while Ax =+0.0001, as before, then -+0,0001 ae) = 0.169% 10-2 0.0878 80 = 7.4112x 10 )@0)( so that only two significant figures are justified: © should be siven as 7.4% 10° RULE 6. The number of significant digits in x determines the number of decimal places (the mantissa) in log x, and conversely. EXAMPLE 1.10 In a certain solution, [H"] = 3.75» 10-* (reat pH = ~log [H"] = -0.574— Here, three decimal places are kept in the mantissa (0.574) because [H*] is given to three significant digits (3.75). On the other hand, if itis given that pH™= 10.7, then € to a Standard state of 1 mol/L). Then, 4.426 (er) = 10" 010-4? = x 0" 10 =}x10-=2% 10 where we evaluate the antilog of 0.7 to one significant digit (ince 0:7 has only one decimal place). If Rules 1-6 leave any doubt as to the proper number of significant figures to list for an answer, a ‘good idea is to alter the last digit of the least significant value in the calculation. This will produce a change in the answer, which should then be truncated to include only the highest digit that changes. 1.7 IMPLICIT ASSUMPTIONS. ‘Throughout this Outline: 1, Unless otherwise limited by significant figures, any chemical assumptions underlying a calculation (¢g., that the ionization of X is negligible) must be borne out by that calculation to within 1%. If an assumption is not validated to better than 1%, it will be dropped and the calculation will be made without it.10 ANALYTICAL AND MATHEMATICAL REVIEW ICHAP. 1 2. Ionic solutions and gases will be assumed to be ideal unless otherwise stated. The activities of solids will be assumed equal to 1.00. 3. A temperature of 25°C will be assumed unless otherwise stated. Solved Problems CONCENTRATIONS 1.1 A blood serum sample is analyzed and found to contain 102.5 wg Ca?"/mL serum. The density of the serum is 1053 kg/m’; AW Ca= 40.08. What is the Ca concentration, in terms of (a) molarity? (6) meq Ca’/L serum? (c) ppm Ca” by wt? 102.5% 10% g 1 mol 1" 4008 102.5 mg Ca” 2 meq Ca “TLserum 40,08 mg Ca (@) 55710" M @) = 5.115 meq Ca®/L serum 1025 wg Co Ambserum oa a Cy eT aey pea = 97.34 sg Cal" Ig serum = 97:34 ppm by wt 1.2 Laboratory A reported the magnesium (AW=24.31) content of a solution (density = 0.985 g/mL) as 194 ppm by wt, whereas laboratory B reported the magnesium content of another sample of the same solution as 8.15 millimolar. Which laboratory measurement was the larger? Using data from A: 985 g soln 194% 10% g Mg_1 mmol Mg TLsoln — gsoln 0.02431 g Mg 86 mmol Mg/L. soln ‘Therefore the B measurement was the larger. 1.3. How many grams of FeSO, (NH,),SO, -6H,0 (MW = 392.14) must be dissolved and diluted to 250.0 mL to prepare an aqueous solution, of density 1.00 g/mL, that is 1.00 ppm Fe® by wt? (AW Fe = 55.85.) 250.0 mL 1.00 g soln, 1.00% 10° g Fe" 392.14 g empd 1 mL soln 1g soln 55.85 g Fe = 1.76% 10" g empd 1.4 How many mL of 2 0.250 M KCI solution must be diluted to 1,000 L so that the diluted solution (density = 1.00 g/mL) is 400 ppm K* by wt? (MW KCI = 74.55; AW K = 39.10.) 1000 g 1.5 How many mL of 0.250 M Fe™ is needed to reach the equivalence point in the titration of 20.00 mL. of 0.100 M Sn?*? ‘The redox reaction is 2Fe™ + Sn? 2Fe™ + Sut Sn’ is oxidized, with my = . whereas Fe™ is reduced, with n,= 1. By (1.3), 240.100)(20.00)= 1(0.250)V, or 160 mL.CHAP. 1] ANALYTICAL AND MATHEMATICAL REVIEW uw 1.6 How many mL of 0.125 M Cr must be reacted with 12.00 mL of 0.200.M MnO, if the redox products are Cr,0,*" and Mn?*? Cr* is oxidized 10 Cr,0;" (Cr oxidation stat is reduced to Mn™, so that n= 5. By (J.3), 3(0.125)Vs = 5(0.200)(12.00) or “+6/C1), so that n, = 3; MnO (oxidation state= +7) 22.0 mL. 1.7 How many milliequivalents of Cr and of MnO, are involved in the reaction of Problem 1.6? By (1.2), the CP* normality is N = 3(0.125) = 0.375, so that meqs CP* = NV(mL) ~ (0.375)32.0 By definition, meqs MnOs must also equal 120, as may be checked by ealeulating the product of normality and volume for MaQe 20 BALANCING REDOX EQUATIONS 1.8 Balance the redox equation where H,S reacts with UO," in an acidic solution to produce $(s) and UY ‘The oxidation state of sulfur is ~2 in HaS and zero in S(s), so that there is an oxidation change of 42/8 = +2/HS. The oxidation state of uranium is +5 in UO;* and +4 in U, so that there is a change in ‘oxidation state of ~1/U = ~1/UO;*. Balancing the oxidation and reduction changes requites that 1H.S react with 2UOs", giving the partially balanced equation HS + 2U02" > S(s)+2U* We now must balance any two of H, O, and charge, using H* and/or HO. The best choice is oxygen ‘and charge, since hydrogen appears in both H’ and HO. Since there are 4 oxygens on the left in the partially balanced equation and none on the right, add 4H0 to the right to balance the oxygen. Since the charge is +2 on the left and +8 on the right, add 6H" to the left to balance the charge, The completely balanced equation is then 6H" + HAS + 2U03" + 8(s) +2" +4H,0 ‘Asa check, there are 8 hydrogens on either side of the equation 1.9 Complete and balance the redox equation where MnO, reacts with NH,OH in a basic solution to produce NO, and MnO,(3), ‘The manganese is +7 in MnO” and +4 in MnOs, so that the reduction is -3/Mn = —3/MnO.°. The nitrogen is ~3 in NH4OH and +5 in NOx, so that the oxidation is +8/N = +8/NH,OH. Balancing the ‘oxidation and reduction changes requires that 8MnOy- react with 3NHJOH, and the partially balanced ‘equation is: SMnOy +3NH,OH=8Mn0,(s)+3NOs ‘Two of the remaining three quantities, H, O, and charge, must be balanced using HO and/or OH” as needed. Since H and O appear in both OH” and HO, it is easiest to balance charge first. The partially balanced equation shows a total charge of 8 on the left and ~3 on the right, so that adding SOH to the right will balance the charge. We can now balance either H or O by adding HO as appropriate. Using H as the basis, we find) 15H on the left and SH (from the added SOH") on the right, ‘Therefore, adding SHO to the right will balance H, yielding the completely balanced equation 8MnOx + 3NH,OH>8Mn0,(s)+3NOs +5OH” +5H:0. ‘The oxygen balance may be checked to confirm that the equation is correct, ic solution to 1.10 Complete and balance the equation where Cr,0; * reacts with H,SO, in an aci produce Cr'* and HSO,12 112 113 ANALYTICAL AND MATHEMATICAL REVIEW [cHaP. 1 Each chromium is +6 in Crs0?- and +3 in Cr, so that the reduction is ~3/Cr = ~6/Cr.0 (ince there are two chromium atoms per Crs0;*). The sulfur is +4 in HaSOs and +6 in HSO.-, so that the oxidation is +2/S = +2/H,SO,. Balancing the oxidation and reduction changes requires 3H:SO, reacting for every Cr,0;* ; the partially balanced equation is: ChO# + 3H,SO)>2CP* + 3HSO¢ Of the remaining three quantities that must balance (H, , charge), it is easiest to balance O and charge. There are 16 oxygen atoms on the left and 12.on the right in the partially balanced equation, so that 4H:0 must be added to the right to balance oxygen. The charge on the left ig ~2 and on the right +3, so that the addition of SH on the left will balance the charge. The final equation, (C10 + 3H:SO, + SH" +2Ce"* + 3HSO." + 41,0 ‘may be checked by a hydrogen balance. Complete and balance the equation where MnO,” reacts with CH,OH in an acidic solution to produce Mn** and CO,(g). ‘The manganese is +7 in MnOs” and +2 in Mn®*, so that the total reduction change is —5/Mn =S/MnO.-. Bach carbon is ~2 in C:H\OH and +4 in COs, so that the oxidation change is +6/C +12/CHsOH. Balancing the oxidation and reduction changes requires 12MnO. reacting with SCH.OH: 12MnOr SCHOH > 12Mn** + 10CO.(g) As the two remaining quantities to be balanced, itis best to choose oxygen and charge. Since there are S3 oxygen atoms on the left but only 20 on the right, 33H0 must be added to the right to balance the oxygen. Since the charge is ~12 on the left and +24 on the right, 36H" must be added to the left 10 balance the charge. The completely balaneed equation is: 12MnO¢ + SC3H6OH+ 36H > 12Mn** + 10CO3 (g)+33H,0 ‘The hydrogen balance will serve as a check Complete and balance the equation where CO(NH,); reacts with OBr’ in an alkaline solution to produce CO,, N;, and Br ‘The nitrogen is -3 in CO(NH,)2 and zero in No, sO that there is an oxidation change of +3/N = +6/CO(NH2):. The bromine is +1 in OBr and ~1 in Br°, so that there is a reduction change of -2/Br = -2/OBr-. Balancing these changes requires that 30Br~ react with each CO(NH)s, $0 that the partially balanced equation is CO(NH:):+30Br + CO.+N.+3BF- ‘Two of the remaining three quantities (H, O, charge) must be balanced using OH” andor HzO; its ‘easiest 1 balance charge first. In the partially balanced equation, both sides have a charge of ~3, so that charge is already balanced and OH” need not be added to either side. At most, we need to add HO. Considering H, there are four on the left but none on the right, so that adding 2H,O to the right will balance the hydrogen and yield the completely balanced equation CO(NH)):+ 30Br > CO, +N.+3Br +2H.0 ‘The oxygen balance may be used to confirm that the equation is correct. Complete and balance the equation where Cl, reacts with Ag’ in an acidic solution to yield AgCI(s) and C10, ‘The silvers +1 in both Ag” and AgCl, soit does not undergo oxidation or reduction, Therefore, some fof the Cl must be oxidized and some reduced, Oxidation takes Cl. from the zero state to +5 in CIOs, for a change of +5/CI= +10/Cl. Reduction takes Cis from the zero state to —1 in AgCl, for a reduction change of -1/Cl=~2/Cl. To balance the oxidation and reduction changes requires that we use 1Ch+ 2C1O¢ for every SCls-> 10AgCI. This results in the partially balanced equationCHAP. 1] ANALYTICAL AND MATHEMATICAL REVIEW 13 1Ch+ SCla+ IWAg*+2C10y + 10AgCI(s) where 10Ag* has been added on the left o balance the silver. After division by 2, the equation reads 3Ch+5Ag" > ClOr + SARCIS) ‘Two of the remaining three quantities (H, O, charge) must be balanced using H* and/or HO. It is ‘easiest to balance O and charge. There are no oxygens on the left in the simplified equation, but there are on the right; hence, add 3H;O to the left. There is a charge of +5 on the left and —1 on the right, calling for the addition of 6H” to the right. The balanced equation, 3Ch + SAg! + 3H:0> COs + SARCI(s) + 6H may be checked by a hydrogen balance STOICHIOMETRY 1.14 Normal human plasma contains cations in the following concentrations: Na’, 143 mmol/L; Ca", 2.38 mmol/L; K", 4.51 mmol/L; Mg”, 1.32 mmol/L. If Cl is the only anion present in any appreciable concentration, what is the total weight (ie., mass) of chloride salts of these four cations in 10.0 mL of human plasma? (MWs: NaCl= 58.44, KCI = 74.55, CaCl, = 110.99, MgCl = 95.22.) Since 10.0 mL is 0.01 L, 1.43 mmol Na” 58.44 mg NaCl 0.0451 mmol K* 74.55 mg KCI 1 T mmol Na* i 1 mmol K* 040238 mmol Ca*_ 110.99 mg CaCl, 0.0132 mmol Mg** 95.22 mg MgC a 1 1 T mmol Mg* = 90.8 mg salts 1.15 The iron, tin, and titanium in a sample were jointly precipitated as hydroxides, which were washed and ignited to produce FeO; SnO;, and TiO;. This mixture of oxides, which amounted to 0.3768 g, was dissolved after fusion with potassium pyrosulfate. Analysis showed that 0.0322 g of Ti was present. The iron was determined separately as an oxide: 0.1837 g FeO was found. What was the weight (mass) of tin in the sample? Molecular and atomic weights are: Ti= 47.90, TiO2= 79.90, Sn= 118.69, SnO2 = 150.69, FeO = 71.85, FesOs= 159.69. If x= g of Sn in sample, then 0.1837 g 9.69 ¢ Fi L 27.85 g FeO) Solving, x = 0.0937 g Sn 1.16 Silver arsenate, AgAsO,, is very insoluble. What weight of Ag,AsO, precipitate forms when 27.00 mL of 0.180 M AgNO, is mixed with 15.00 mL. of 0.130 M Na,AsO,? The reaction is 3Ag' + AsOx'-— AgsAsO4(s). The molecular weight of AgsAsOs is 462.6. The mixture contains (0.180)(27.00)= 4.86 mmol Ag™ and (0.130)(15.00) = 1.95 mmol AsO. Since three times as much Ag" is needed as AsO”, the Ag” is the limiting reagent; thus, 486 = 1.62 mmol AgsAsOs is formed (and 1.95~ 1.62 = 0.33 mmol AsO,” is left over). Consequently (1.62 mmol Ag,As0,)(462.6 mg AgsAsO,/mmol AgysO,) = 749 mg AgsASOs