Solutions Manual for Harris’ Quantitative Chemical Analysis Seventh Edition Daniel C. Harris Michelson Laboratory W. H. Freeman and Company New YorkISBN: 0-7167-7260-4 EAN: 97807167-7260-6 © 2007 by W. H. Freeman and Company All rights reserved, Printed in the United States of America First printing W.H. Freeman and Company 41 Madison Avenue ‘New York, NY 10010 Houndmills, Basingstoke RG21 6XS England ‘wow.whfteeman.comContents Chapter 0 Chapter 1 Chapter 2 Chapter 3 Chapter 4 Chapter 5 Chapter 6 Chapter 7 Chapter 8 Chapter 9 Chapter 10 Chapter 11 Chapter 12 Chapter 13 ‘Chapter 14 Chapter 15 Chapter 16 Chapter 17 Chapter 18 ‘Chapter 19 Chapter 20 Chapter 21 Chapter 22 Chapter 23 Chapter 24 Chapter 25 Chapter 26 Chapter 27 Chapter 28 The Analytical Process Measurements Tools of the Trade Experimental Error Statistics Quality Assurance and Calibration Methods Chemical Equilibrium Let the Titrations Begin Activity and the Systematic Treatment of Equilibrium Monoprotic Acid-Base Equilibria Polyprotic Acid-Base Equilibria Acid-Base Titrations EDTA Titrations Advanced Topics in Equilibrium Fundamentals of Electrochemistry Electrodes and Potentiometry Redox Titrations Electroanalytical Techniques Fundamentals of Spectrophotometry Applications of Spectrophotometry Spectrophotometers Atomic Spectroscopy Mass Spectrometry Introduction to Analytical Separations Gas Chromatography High-Performance Liquid Chromatography Chromatographic Methods and Capillary Electrophoresis Gravimetric and Combustion Analysis Sample Preparation 10 14 20 34 47 58 69 7B 89 103 130 146 176 139 201 216 228 235 246 253 261 276 289 301 314 331 3410-1. 0-2. 0-5. CHAPTER 0 THE ANALYTICAL PROCESS Qualitative analysis finds out what is in a sample. Quantitative analysis measures how much is in a sample. Steps in a chemical analysis: @ Q) @) 4) 6) © aM Formulate the question: Convert a general question into a specific one that can be answered by a chemical measurement. Select the appropriate analytical procedure. Obtain a representative sample. Sample preparation: Convert the representative sample into a sample suitable for analysis. If necessary, concentrate the analyte and remove or mask interfering species. ‘Analysis: Measure the unknown concentration in replicate analyses. Produce a clear report of results, including estimates of uncertainty. Draw conclusions: Based on the analytical results, decide what actions to take. Masking converts an interfering species to a noninterfering species. ‘A calibration curve shows the response of an analytical method as a function of the known concentration of analyte in standard solutions. Once the calibration curve is known, then the concentration of an unknown can be deduced from a measured response. (a) (b) © ‘A homogeneous material has the same composition everywhere. In a heterogeneous material, the composition is not the same everywhere Ina segregated heterogeneous material, the composition varies on a large scale, There could be large patches with one composition and large patches with another composition. The differences are segregated into different regions. In a random heterogeneous material, the differences occur on a fine scale. If we collect a "reasonable-size" portion, we will capture each of the different compositions that are present. To sample a segregated heterogeneous material, we take representative amounts from each of the obviously different regions. In panel b in Box 0-1, 66% of the area has composition A, 14% is B, and 20% is C. To construct a0-6. Chapter 0 representative bulk sample, we could take 66 randomly selected samples from region A, 14 from region B, and 20 from region C. To sample a random heterogeneous material, we divide the material into imaginary segments and collect random segments with the help of a table of random numbers, ‘We are apparently observing interference by Mn2* in the F- analysis by method A. The result of the I- analysis is affected by the presence of Mn2+. The greater the concentration of Mn2* in the mineral water, the greater is the apparent concentration of I found by method A. Method B is not subject to the same interference, so the concentration of is low and independent of addition of Mn?+. There must be some Mn?* in the original mineral water, which causes method A to give a higher result than method B even when no Mn?* is deliberately added.1 1-4, 15. CHAPTER 1 MEASUREMENTS [4 note from Dan: Don’t worry if your numerical answers are slightly different from those in the Solutions Manual. You or I may have rounded intermediate lresults. In general, retain many extra digits for intermediate answers and save our roundoff until the end. We'll study this process in Chapter 3. (a) meter (m), kilogram (kg), second (s), ampere (A), kelvin (K), mole (mol) (b) hertz (Hz), newton (N), pascal (Pa), joule (J), watt (W) See Table 1-3. Prefixes above kilo are capitalized: Mega (106), Giga (10°), Tera (1012), Peta (1015), Exa (1018), Zetta (102!) and Yotta (104). (@) mW = milliwatt, = = 10-3 watt (b) pm = = _picometer 10-12 meter (@kQ = kiloohm = = ~—108 ohm (@) WF =~ microfarad «== = 10 farad ©T = terajoule = = ~—10! joule (Ons = nanosecond = — 10-9 second (g) fg = femtogram = 10°15 gram (h) Pa = decipascal = 10°! pascal (a) 100 £9 or 0.1 pI (@) 0.1 nm or 100 pm (b) 43.1728 nF (© 21TW (©) 299.79 THz or 0.299 79 PHz (f) 0.483 amol or 483 zmol ikg 54Pg=54x10I5g, 54x 1015 =5.4x 1012 kg of C (@) 5.4Pg=5.4x 1015 g. x 105 fx 000 x 1012 kg of (b) The formula mass of CO is 12.010 7 + 2(15.999 4) = 44.009 5 44,0095 g CO, 5.4 x 10!2 ky x 40005 £ CO = 2.0 x 10! kg CO; * ef 12.0107 pe * chen Lton 2.0 x 1013 jf CO2 x = 2.0 x 10!0 tons of CO; © E COr 7000} ns of CO 2.0x10"° tons = = 41tons per person 5x10” peopleChapter 1 7.457 x 104 Is. 100.0 horsepower = (000 ssa rasraiot a ‘ Gh *3:600F = 6416x107 = 4.184 — cal (2 x0 ( (4 1-7. (a) = 2.0 J(skg) kg (20s 6— ) = 2.0 Wikg Similarly, 3.4 x 103 as 3.0 J(s:kg) = 3.0 Wikg. lay (b) The office worker’s power output is wn ‘The person consumes more energy than the 100 W light bulb. 1x 1022 =11x102W 5 0.0254 m 18 (@) “Tinch » (asaf SES (es) = oziatile (0 a14t2|(aeend) = 770 mile/n (772 if you did not round off 0.214) 1 Finch = * = 39.37 inches s © e0rA(ms3) = 1.04% 103 m = 1.04 km pm a a a {s0s10 2055 ote (53 0.643 mile =147x108 4 = 147x108 W s 1-10. Newton = force = mass x acceleration = (3) sMeasurements 1-1. 1-12. 1-13. 1-14. 1-15. 1-16. Joule = energy = force x distance = wf Pascal = pressure = force/area = is om Aa lors (ma) i |r) (a) molarity = moles of solute / liter of solution ton (b) molality = moles of solute / kilogram of solvent (©) density = grams of substance / milliliter of substance (@) weight percent = 100 x (mass of substance/mass of solution or mixture) () volume percent = 100 x (volume of substance/volume of solution or mixture) (parts per million = 106 x (grams of substance/grams of sample) (g)_ parts per billion = 10° x (grams of substance/grams of sample) (h) formal concentration = moles of formula/liter of solution Acetic acid (CH3CO2H) is a weak electrolyte that is partially dissociated. When we dissolve 0.01 mol in a liter, the concentrations of CH3CO2H plus CH3CO3 add to 0.01 M. The concentration of CH3CO2H alone is less than 0.01 M. 32.0 g / [(22.989770 + 35.453) g/mol] = 0.548 mol NaCl 0.548 mol /0.500L = 1.10M " 0.171 mol CH30H mol CH30H 1.712 = |(0.100 Lsoletton) ( malcoe | (on sescrsc | 2OtE | Bs 548 g (a) 19 mPa=19x103Pa, 19x 103 Pf x Iba 1.9.x 10-7 bar 10° Pe (b) T (K) = 273.15 + °C = 273.15 - 70 = 203 K1-17. 1-18. 1-19, 1-20. 1-21. 1-22, Chapter 1 P x10~ te 2x = 11x108M = 11nM 0.083 wn x 203K 1g solute 7 i : aad 1 ppm = 796% sotution’ Since 1 L of dilute solution ~ 103 g, 1 ppm = 10°3 g solute/L (= 10°3 g solute / 103 g solution). Since 10°3 g = 103 ug, 1 ppm = 103 g/L or 1 ug/L. Since 10°3 g = 1 mg, 1 ppm = 1 mg/L. 0.2 ppb means 0.2 x 10 g of CooH4 per g of rainwater BCr0Hy2 (0.2 x 10 g Coola 1000 g rainwater ~~ L rainwater 0.2x10 g/L = 7x 1010M 282.55 g/mol (oms.2800s | (37.6 gsoknton) = 26.5 g HCIO, gsolation | 37.6 g solution ~ 26.5 g HCIO4 = 11.1 gH20 (@) (1sr822u22\ oo = 0.2x 106 1.67 x 103 g solution aa (b) (o7s£800s Jo X10° gsoktion) = 1.18 x 103 g HCIO, ion (©) (1.18 x 103 £)/(100.46 g/mol) = 11.7 mol . mol KI molality = Grrowent _ _200gKI___ 200g KI 20.0 wt% KI = 7909 g solution = 800 g 120 To find the grams of KT in 1 kg of H2O, we set up a proportion: 200gKI__ _x gkI _ 800 gH20 = 1000gH20 >* = 250gKI But 250 g KI = 1.51 mol KI, so the molality is 1.51 m. (@) (150.10 25) [asso } 6.0 amol/vesicle ol‘Measurements 1-23. 1-24, 1-25. (b) 6.0x10718 se ( sana! = — 3.6 x 108 molecules (©) Volume = £n(200 x 109 m)3 = 3.35 x 10°20 m3; 3.351070 sh? ZA = 3.35x 10177 103 yf /L 18 cg) 1x10 mol _ 930M 3.35x107°"L 80x10 y4 80x10" £ gato mo, 2410 mol 445 103M; 180.2 ¢/mol 100x10°L Similarly, 120 mg/100L = 6.7 x 103M (a) Mass of 1.000L = ote E> x 1 000 x 10002 = 1046 g pat x sa £ Grams of CoH, liter = 6.0672 x 62.07 3766 rams of C2H¢03 per liter x 0207 Ne = S166 (b) 1.000 L contains 376.6 g of CzH¢02 and 1 046 ~ 376.6 = 669 g of H20 = 0.669 kg 6.067 mol CoH602 mol CpH¢02 Molality = “Tea7 Kg 1QO = 9° “keto = 92.07 m Shredded aes 1.000 g contains 0. 7 g protein + 0.799 g carbohydrate 0.099 f x40 rie 0.799 ¢ x40 Z = 3.6Cal Doughnut: 1,000 g contains 0.046 g protein + 0.514 g carbohydrate + 0.186 g fat Cal Cal 0.046 £ x4.0 Z +0514 g x40 ie 0.186 ¢ x 9.0 ay = 3.9Cal ic Ina similar manner, we find 2.8, ra for hamburger and 0.48 a for apple. ‘There are 16 ounces in 1 pound, which Table 1-4 says is equal to 453.592 37 g To convert Cal/g to Cal/ounce, multiply by 28.35: Shredded Wheat__Doughnut__Hamburger__Apple Calg 36 39 28 0.48 Calfounce 102 ut 9 41-26. 1-27. 1-28. 1-29. 1-30. Chapter 1 Shredded Wheat Doughnut __Hamburger___ Apple Cal/g 36 39 28 0.48 Cal/ounce: 102 1 79 14 Mass of water = 1 (225 pt)? (10.0 yf) 1.59 x 109 kg _ 16x103 gF 1.6 ppm = "Ke 0 Mass of F required = (19:00 cre ig 0000 sett) = 25x 105 gF. (If we retain three digits for the next calculation, this last number is 2.54 x 106) Now the atomic mass of F is 18.998 and the formula mass of NaF is 41.988, mass of F 2.54 x 106 gF mass of NaF = TENER 4 = 5.6% 105g NaF (a) PV = nRT (1.000 bar)(5.24 x 1061) = n (oo EB ee ovsasi mol -K =>n =2.11 x 10-7 mol => 2.11 x 107M. (b) Ar: 0.934% means 0.009 34 L of Ar per L of air (1.000 bar)(0.009 34 L) = n (00ss 14 a (298.15 K) )« ) => n=3.77 x 104 mol = 3.77 x 104M Kr: 1.14 ppm => 1.14pLKrperLofair = 4.60x 108M Xe: 87 ppb => 87nL Xe perLofair => 35x 109M 2.00 10050029. 6183- 83-8, = 6.18 gin a2L volumetric flask Weigh out 2 x 0.0500 mol = 0.100 mol = 6.18 g B(OH)3 and dissolve in 2.00 kg H20. Meon* Veon = Mait Vait (2024 a0 XY) = (ose!) Vai => Vain = 3.2L‘Measurements 1-32. 1-33. 1-34. 1-35. 10 gO 8.0 g solution 0.50. goon gsolution Mail x @) Veon = Veit ace = 1000 mL. Ge i) = 55.6 mL (b) One liter of 98.0% Hq contains (18.0 sa6f )(98.079 g/ aol) = 1.77 x 103 g of H2SO4. Since the solution contains 98.0 wt% H2SOx, and the mass of H2SO, per mL is 1.77 g, the mass of solution per milliliter (the density) is LTT /mL SLB IML _ 5 g solution/mL 0.980 g He80q /g solution 2.00 L of 0.169 M NaOH = 0.338 mol NaOH = 13.5 g NaOH __ solution density = Tar solution 13.5 g Naor eee = ees ts (16.7 mL solution) [oss sso ] g solution FM of Ba(NO3)2 = 261.34 4.35 g of solid with 23.2 wt% Ba(NOs)2 contains (0.232)(4.35 g) = 1.01 g Ba(NOs)2 (1.01 g BapNO5yz) mol Batt = ——=—___-__ = 3.86 x 103 mol (261.34 g BatNO5}p / mol) mol Hy$O4 = mol Ba?* = 3.86 x 10-3 mol .86 x 103 mol, volume of H2SO, = Sooty = 1.29 mL 25.0 mL of 0.023 6 M Th** contains (0.025 0 L)(0.023 6 M) = 5.90 x 10-4 mol Th4* mol HF required for stoichiometric reaction = 4x mol Th4* = 2.36 x 10°3 mol 50% excess = 1.50(2.36 x 10°3 mol) = 3.54 x 10°3 mol HF Required mass of pure HF = (3.54 x 10-3 mol)(20.01 g/mol) = 0.0708 g (0.0708 guf Mass of 0.491 wt% HF solution = 0.0708 HF) = 144g (0.004 91 g HF’ /g solution)21. 2-3, 24, 25. 2.8. 2-10. 2-11. CHAPTER 2 TOOLS OF THE TRADE ‘The primary rule is to familiarize yourself with the hazards of what you are about to do and not to do something you consider to be dangerous. PbSi03 is insoluble and will not leach into ground water. ‘The upper "0" means that the reagent has no fire hazard. The right hand "0" indicates that the reagent is stable. The "3" tells us that the reagent is corrosive or toxic and we should avoid skin contact or inhalation, The lab notebook must: (1) state what was done; (2) state what was observed; and (3) be understandable to a stranger. See Section 2.3, ‘The buoyancy correction is | when the substance being weighed has the same density as the weights used to calibrate the balance. 0.001 2 g/mL (14.82 g) (i — 20 2 ain) m= 7 qpoi2 yim) = 485s —"0.626 g/mL ‘The smallest correction will be for PbO2, whose density is closest to 8.0 g/mL. ‘The largest correction will be for the least dense substance, lithium. 0.001 2 g/mL 4.2366 i -“a.0gmL m= coupagnry ~ = 4218 1~"7.636 g/mL Without correcting for buoyancy, we would think the mass of primary standard is, Jess than the actual mass and we would think the molarity of base reacting with the standard is also less than the actual molarity. The percentage error would be true mass ~ measured mass 4.239 1 ~ 4.2366 = 100 = “Fas 7- x 100 = 0.06%. (a) One mol of He (= 4.003 g) occupies a volume of 10Tools of the Trade ul 2-12. 2-13. 214, 2-15. 2-16. 2-17. 2-18, 2-19. op (nonare LP \a.5 x) 1s 1 nRT v = 24.37L Density = 4.003 g/ 24.37 L = 0.164 g/L = 0.000 164 g/mL 0.000164 gat” corre 1- Swe) a 000 164 gle 0.97 glen (a) (0.42) (2330 Pa) = 979 Pa () Air density (0.003 485)(94 000) — (0.001 318)(979) _ = ws = LI gL = 0.0011 gimL 0.0011 gle wate | _ 10010 100011 gil _ 1.00 gi a 6 370 000 m)> mp = mg (100.0000 eso oD = 99.999 1g (b) m= 0.823 g (©) mass = 1.0000 g TD means "to deliver" and TC means "to contain.” Dissolve (0.2500 L)(0.1500 mol/L) = 0.037 50 mol of KSOg in less than 250 mL of water in a 250-mL volumetric flask. Add more water and mix. Dilute to the 250.0 mL mark and invert the flask many times for complete mixing. ‘The plastic flask is needed for trace analysis on analytes at ppb levels that might be lost by adsorption on the glass surface. See Section 2.6. Transfer pipet. ‘The trap prevents tap water from backing up into the suction flask. If you use house vacuum, the trap prevents solution from the filtration from being sucked into the house vacuum system. The watchglass keeps dust out of the sample.12 2.20. 2-21. 2.22. 2.23, 2-24. 2.25. Chapter 2 Phosphorus pentoxide 20.2144 g— 10.2634 g = 9.9510 g. Using column 3 of Table 2-7 tells us that the true volume is (9.9510 g)(1.0029 mL/g) = 9.979 9 mL. 0.999 102: Expansion = pooes = 1.002060 8 = 0.2%. Densities were taken from Table 2-7. The 0.5000 M solution at 25° would be (0.5000 M)/(1.002) = 0.4990 M. Using column 2 of Table 2-7, mass in vacuum = (50.037 saf)(0.998 207 1 g/ ya) = 49.947 g. 50.037 yt Using column 3, mass in air = =! 90 = 1.0029 yail/g = 49,892 g. ‘When the solution is cooled to 20° C, the concentration will be higher than the : density at 20°C concentration at 24° C by a factor of Sensinparga°c- Therefore, the concentration needed at 24° will be lower than the concentration at 20° C. 0.997 299 5 gla Desired concentration at 24°C = (1.000M) | °° | _ g.9991 m 0.998 207 1 gaff (using the quotient of densities from Table 2-7). The true mass of KNO3 needed is (0.5000 ¥) (os 24 ror. x (50.506 g) m ( 0.001 2 g/ml.’ 1-30 g/mL Al extracted from glass = (0.200 L)(5.2 x 106 M) = 1.04 x 10-6 mol mass of Al = (1.04 x 10-6 mol)(26.98 g/mol) = 28.1 wg This much Al was extracted from 0.50 g of glass, so 28.1 x 10-6 wt% Al extracted = 100 xe ee = 0.005 6 wt% 0.005 6 wt% Fraction of Al extracted = 9 gq qqqq = 9.007 0 (or 0.70% of the Al)Tools of the Trade 2-26. (Graph of van Deemter Equation Fiow rate _|Plate height Constants |(mL/min) — |(mm) A= | 8.104] 7.65) G 6.099] B= 3 5.064] 25.8 10] 4.466 c= 20| 3.412] 0.0236 30] 3.218] 40] 3.239) 50| 3.346] 60| 3.496! 70| 3.671 80| 3.861 90| 4.081 To9| 4.268] (Formula: |AS6+SASB/B5+$ASI0°BS Plate height (mm) van Deemter Equation Flow rate (mL/min) . r r 1331. 3-2, 33. 3-4. 35. 3-9, 3-10. 3-11, 3-12. CHAPTER 3 EXPERIMENTAL ERROR (a5 (b) 4 (©) 3 (a) 1.237 (b) 1.238 ©) 0.135 @) 2.1 (e) 2.00 (a) 0.217 (b) 0216 © 0.217 (b) 1.18 (significant figures) (c) 0.71 (2 significant figures) @ 371 (b) 10.7 ©) 40x10! a) 2.85x 106 (e) 12.625 1 (f) 6.0 x 104 (g) 242 (a) BaF) = 137.327 + 2(18.998 403 2) = 175.324 because the atomic mass of Ba has only 3 decimal places. (b) CeHl4O4 = 6(12.0107) + 4(1.007 94) + 4(15.999 4) = 140.093 5 (The fourth-decimal place in the atomic mass of C has an uncertainty of #8 and the fourth-decimal place of O has an uncertainty of + 3. These uncer- tainties are large enough to make the fourth-decimal place in the molecular ‘mass of CoH4Og insignificant. Therefore, a good answer is 140,094.) (a) 123 (b) 75.5 (©) 5.520 x 103 (a) 3.04 (©) 3.04x 1010 (fH 11.9 (g) 4.600 (b) 4.9 x 107 All measurements have some uncertainty, so there is no way to know the true value, Systematic error is always above or always below the “true value” if you make replicate measurements. In principle, you can find the source of this error and climinate the error in a better experiment so the measured mean equals the true mean. Random error is equally likely to be positive or negative and cannot be eliminated. Random error can be reduced in a better experiment. ‘The apparent mass of product is systematically low because the initial mass of the (crucible plus moisture) is higher than the true mass of the crucible. The error is, systematic. ‘There is also always some random error superimposed on the systematic error. (a) 25.031 mL is a systematic error. The pipet always delivers more than it is 14Experimental Error 15 3-13. 3-14, 3-15. @ rated for. The number + 0,009 is the random error in the volume delivered. The volume fluctuates around 25.031 by # 0.009 mL. ‘The numbers 1.98 and 2.03 mL are systematic errors. The buret delivers too little between 0 and 2 mL and too much between 2 and 4 mL, The observed variations +0.01 and +0.02 are random errors. The difference between 1.9839 and 1.9900 g is random error. The mass will probably be different the next time I try the same procedure. Differences in peak area are random error based on inconsistent injection volume, inconsistent detector response, and probably other small variations in the condition of the instrument from run to run, Carmen (b) Cynthia (¢) Chastity (d) Cheryl 3.124 (40.005), 3.124 (40.2%). It would also be reasonable to keep an additional digit: 3.1236 (40.0052), 3.1236 (#0.17%) (a) (b) 6.2 (40.2) =4.1 (40.1) 21 te — e2= 0,240.12 = e=0.22 Answer: 2.1 +0.2 (or 2.1 # 11%) 9.43 (£0.05) 9.43 (40.53%) 0.016 (40.001) => 0.016 (46.25%) — %e? = 0.53? + 6.25? 0.15088 (+ %e) => %e = 6.272 Relative uncertainty = 6.27%; Absolute uncertainty = 0.150 88 x 0.0627 = 0.009 46; Answer: 0.151 #0.009 (or 0.151 + 6%) (c) The first term in brackets is the same as part (a), so we can rewrite the (d) problem as 2.1 (+0.224) + 9.43 (40.05) = 2.1 (#10.7%) + 9.43 (40.53%) %e = 10.7? +0.532 = 10.7% Absolute uncertainty = 0.107 x 0.223 = 0.0239 Answer: 0.223 +0.024 (#119) ‘The term in brackets is 6.2 (40.2) x 10 e=V0.22+0.12 => ©=0.224 (40.1) x 103 10.3 (0.224) x 103 = 10.3 x 10°3 (42.17%) 9.43 (40.53%) x 0.0103 (#2.17%) = 0.097 13 #2.23% = 0.097 13 +0.002 17 Answer: 0.097; + 0.0022 (+ 2.2%)16 3-16. 3-17. Chapter 3 (a) Uncertainty =o. 03? + 0.02? +.0.062 = 0.07 Answer: 10.18 (40.07) (40.7%) (b) 91.3 (41.0) x 40.3 (£0.2)/21.1 (40.2) = 91.3 (41.10%) x 40.3 (40.50%)/21.1 (40.95%) % uncertainty = 1.102 + 0.502 + 0.952 = 1.54% Answer: 174 (43) (42%) (©) [4.97 (40.05) — 1.86 (20.01)/721.1 (40.2) = [3.11 (£0.0510)]/21.1 (40.2) = [3.11 (£1.64%)V/21.1 (40.95%) ).147 (1.90%) = 0.147 (20.003) (#2%) @ — 2.0164 (40.0008) 1.233 (40.002) + 4.61 (20.01) 7.8594 V(0.0008)2+(0.002)2+(0.01)2 = 0.0192 Answer: 7.86 (40.01)(40.1%) © 20164 (20.8) + 123.3 (40.2) + 46.1 (40.1) 2185.8 (082+ O.22+ (1? = 08 ‘Answer: 2 185.8 (20.8) (40.04%) () Fory=24, ey = a%ex 23.14 £0.05 => %ey = (0.05 /3.14) x 100 = 1.592% Sey = ¥ (1.592%) = 0.531% Answer: 1.4643 + 0.007s (40.53%) (@) Fory=log x, ey =0.43429 x=3.14£0.05 = ey = 043420 Answer: 0.4969 + 0.0069 (+ 1.39%) = 0.006915 0.017 5% (@) y = x12 = %ey = $(100.« (1.75 x 10-4) 3.1415 = 0.0011 (b) y = logx => ey = 0.43429 Qt 3) 0.0011 3.1415, 1x 104 Answer: 1.77243 + 0.0003; 1.52 x 104Experimental Error 7 Answer: 0.497 14 0.000 1s ©y intilog x= 10* => ey=y x 2.3026 e = (103-141 5)(2.302.6)(0.001 1) = 3.51 Answer: 1385 + 0.0035 x 103 0. @y= Ing > 6 = SO = 35x 104 Answer: 1.14479 +0.00035 4 (006 .006 (©) Numerator of log term: y = x2 => ey = 7(G 794% 100 0.322542.88% _ 0,3225+2,88% 0.0511£0.0009 ~ 0.0511+1.76% = 6.311 +3.375% = 6.311+0.213 2.88% For y= log.x,ey = 0.43429 % = = 0.43429 (383) = = 0.015 Answer: 0.80 #0.015 3-18. C: 12.0107 + 0.0008; H: 1.00794 + 0.00007; O: 15.9994 + 0.0003; N: 14,0067 + 0.0002 +9C: 912.0107 + 0.0008) +9H: 9(1.007 94 + 0.00007) +60: 6(15.9994 + 0.0003) 95.996 4 + 0.001 8 43N: _3(14.0067 + 0.0002) 42.020 1 + 0.0006 CoH9O6N3: 255.184 26+? Uncertainty = +f0.007 2? + 0.000 63? + 0.001 8? + 0.000 6? = 0.007 47 Answer: 255.184 + 0,007 108.096 3 + 0.007 2 9.071 46 + 0.000 63 3-19. (a) Na = 22.989770 + 0.000002 g/mol Cl = 35.453, +0.002 g/mol 58442770 -V(2 x 10°)2 + (2x 10°32 = 2x 103 58.443 + 0.002 g/mol mol _ [2.634 (£0,002)g] / [58.443 (£0.002)g/mol] (b) molarity = “T= (0.100000 (0.00008) L = 2.634 (40,0769) / [58.443 (40.003 4%) 0.100 00 (0.08%) relative error = (0.076%)? + (0.003 4%)? + (0.08%)? = 0.11% molarity = 0.4507 (+0.000 5)M18 3-20. 3-21, 3-22. Chapter 3 0,001 2(+0.000 1) g/mL (1.0346 (20.0002) a) (1~ 8.0 0.5) gimL ) ee (0.001 2(40.000 1) g/mL 1~""0.997 2995 g/mL, 0.001 2 (+8.33%)) [1.034 6 (40.019 3%)] (\- 8.0(26.25%) 0.0012 28.33%) 10.997 299 5 (20%) 1,034 6 (40.019 3%)][1 ~ 0.000 150 (410.4%) ae [1 — 0.001 203 (48.33%)] 1,034 6 (40.019 3%) [1 ~ 0.000 150 (+0.000015 6) m= [1 — 0.001 203 (0.000 100)] 1.034 6 (+0.019 3%)] [0.999 850.0 (+0.000 015 6)] ms 10.998 797 (0.000 100)] 1,034 6 (20.019 3%)] {0.999 8500 (#0.001 56%: oa 0.998797 (+0.0100%)] m = 1.0357 (40.021 8%) = 1.0357 (+0.0002) g 0.2774#0.001g2 0.2774 _ 0.001 mol Fe203 = 759.688 g/mol = 159.688 * 159.688 = 1.7371 + 0.0113 mmol Fe703; mass of Fe = 2[1.7371 (40.0113) x 10°3 mol] [55.845 g/mol] = 0.19492 + 0.00126 mass of Fe per tablet = (0.19492 # 0.00126 g)/12 = 16.16 + 0.los mg = 1620.1 mg mol H* = 2 x mol NayCO3 _ 0.9674 (40.0009) g_ _ _0.9674 (+0.093%) g mol NayCO3 = 795.988 (40.001) g/mol = 105.988 (40.000 94%) g/mol = 0,009 127 4 (£0.093%) mol mol Ht = 2(0.009 127 4 (40.093%)) = 0.018 255 (40.093%) mol (Relative error is not affected by the multiplication by 2 because mol Ht and uncertainty in mol H+ are both multiplied by 2.)Experimental Error 19 3-23, larity of HC] = 2.018255 (0.093%) mol _ 0.018255 (#0.093%) mol molarity of HCI = “9.92735 (0.00004) L_ =~ 0.02735 (0.146%) L = 0.66746 (£0.173%) = 0.667 46 (#0.001 155) = 0.667 + 0.001 M To find the uncertainty in co3, we use the function y = x* in Table 3-1, where x= co and a= 3. The uncertainty in co} is 0.000 000 33 Joey = a %ex = 3X 5451 Q90 36 X 100 = 1.823 x 105% So co? = (5.431 020 36 x 10°8 cm)3 = 1.601 932 796 0 x 10-22 m3 with a relative uncertainty of 1.823 x 10°5%, We retain extra digits for now and round off at the end of the calculations. (If your calculator cannot hold as many digits as we need for this arithmetic, you can do the math with a spreadsheet set to display 10 decimal places.) The value of Avogadro's number is computed as follows: msi 28.085 384 2 g/mol © (peo3)/8 ~ (2.329 031 9 gicm? x 1.601 932 7969 x 10°22 cm3)/8 = 6.022 136 936 1 x 1023 mol! Na The relative uncertainty in Avogadro's number is found from the relative uncertainties in msi, p, and co3. (There is no uncertainty in the number 8 atoms/unit cell.) percent uncertainty in ms = 100 (0.000 003 5/28.085 384 2) = 1.246 x 10°5% percent uncertainty in p = 100 (0.000 001 8/2.329 031 9) = 7.729 x 10°5% percent uncertainty in co3 = 1.823 x 10°5% (calculated before) percent uncertainty in Na = | %ems;? + %er? + (Ye c,3)2 = = V(1.246 x 10°5)? + (7.729 x 10°5)? + (1.823 x 10°5)2 = 8.038 x 10°5% ‘The absolute uncertainty in Na is (8.038 x 105%)(6.022 136 936 1 x 1023)/100 = 0.000 004 841 x 1023, Now we will round off Na to the second digit of its uncertainty to express it in a manner consistent with the other data in this problem: Na = 6.022 136 9 (+0.000 004 8) x 1023 or 6.022 136 9 (48) x 102320 41. 43, 4-4, CHAPTER 4 STATISTICS ‘The smaller the standard deviation, the greater the precision. There is no necessary relationship between standard deviation and accuracy. The statistics that we do in this chapter pertain. to precision, not accuracy. (a) to corresponds toz = -1toz = +1. The area fromz = Otoz = +1is 0.341 3. The area from z = 0 to z=—1 is also 0.3413. Total area ( = fraction of population) from z =-1 to z= +1 = 0.6826. (b) z=-2toz=42 => area=2x 0.4773 = 0.9546 (o) z= 3413 @ z=0toz=0.5 = area=0.1915 (e) Area from z=~-1 toz = is 0.3413. Area from z=~-0.5 to z= 0 is 0.1915. Area from z=~1 to z = -0.5 is 0.3413 -0.1915 =0.1498. to z=4+1 => area= (a) Mean = (1.526 60 + 1.52974 + 1.52592 + 1.52731 + 1.52894 + 1.528 04 + 1.52685 + 1.52793) = 1.52767 (b) Standard deviation (c) Variance = (0.001 26)2 = 1.59 x 10-6 (a) 1005.3 hours corresponds to z = (1005.3 ~ 845.2/94.2 = 1.700. In Table 4-1, the area from the mean to z= 1.700 is 0.455 4. The area above = 1.700 is therefore 0.5 - 0.455 4 = 0.044 6. (b) 798.1 corresponds to z = (798.1 - 845.2)/94.2 = -0.500. ‘The area from the mean to z = -0.500 is the same as the area from the mean to z= +0.500, which is 0.191 5 in Table 4-1. 901.7 corresponds to z = (901.7 ~ 845.2)/94.2 = 0.600. The area from the mean to 2 = 0.600 is 0.225 8 in Table 4-1. ‘The area between 798.1 and 901.7 is the sum of the two areas: 0.1915 + 0.2258 = 0.4173Statistics 21 (©) The following spreadsheet shows that the area from —0 to 800 h is 0.315 7 and the area from so to 900 h is 0.719 6. Therefore, the area from 800 to 900 his 0.719 6 - 0.315 7 = 0.404 0. A B c 1 |Mean= _|Stddev= 2| 8452 942 3 4 |Areafrom-=to800= | _0.3187| 5 [Area from == to 900 = 0.7196| 6 [Area from 800 to 800 10.4040] 7 I [C4 = NORMDIST(800,$A$2,S682, TRUE) {9 |C5 = NORMDIST(900,$AS2,$BS2, TRUE) 10 |C6 = C5-C4 4-5. (a) Half the people with tumors have K < 0.92 and would not be identified by the test. The false-negative rate is 50%. (©) The false-positive rate is the fraction of healthy people with K > 0.92. To use ‘Table 4-1, we need to convert x = 0.92 to az value defined as Xap _ 0.92-0.75 zs O97 = 243 In Table 4-1, we find the area from the mean (z = 0) to z= 2.4 is 0.491 8, The area from the mean to z = 2.5 is 0.493 8, We can estimate that the area from the mean to z= 2.43 is a little greater than 0.492. The area above z = 2.43 is therefore 0.5 — 0.492 = 0.008. That is, 0.8% of healthy people will have a false positive indication of cancer. In the following spreadsheet, cell E5 computes the area below K = 0.92 with the formula NORMDIST(0.92, $B$4,SBS5,True), where cell B4 contains K and cell BS contains the standard deviation. The area below 0.92 is found in cell ES to be 0.992 4. The area above K = 0.92 is therefore 1 - 0.0024 = 0.007 6Chapter 4 cy c D Te F @ a [Sanat sorbutantor ‘phase parttioning of plasma proteins 2 [ [Healthy patients For healthy people, [Area below cutoff 4|MeanK=[ 0.75 larea below 0.92 = for people with tumors 5 0.07 0.992421 [Cutoff (K) [Area 6 [Malignant tumor farea above 0.92 : 0.8] 0.137656 Z| Mean K. 088 ~ [0.007879] 0.81] 0.158655] g ont 0.82] 0.181651 area below 0845 = - 0:83| 0.206627] a 0.912632] — 0.84] 0.233529] a = jarea above 0.84% 0.85| 0.26227/ = 0.087368] 0.845] 0.247677| 3 14 |E5 = NORMDIST(0.92,$884,$8$5, TRUE) _[H6 = NORMDIST(G6,$BS7,$B$8,TRUE) | 15/67 =1-€5 47. 48. (©) Incoluma G, we vary the value of K and compute the area above K under the curve for people with malignant tumors in column H. We search for the value of K that give an area of 0.25, which means that 25% of people with tumors will not be identified. The value 0.84 give an area of 0.233 5 and the value 0.85 gives an area of 0.262 3. By trial and error, we find that K = 0.845 gives an area near 0.25. In cell E10, we insert K = 0.845 into the NORMDIST function for healthy people and find that the area below K = 0.845 is 0.912 6. The area above 0.845 is 1 -0.912 6 = 0.087 4, That is, 8.7% of healthy people will produce a false positive result, indicating the presence of a tumor. Use the same spreadsheet as in the previous problem, but vary the standard deviation. Here are the results: 8 600 400 Number of light bulbs 8 600 800 1000 1200 Hours ‘A confidence interval is a region around the measured mean in which the true mean is likely to lie,Statistics 23 4-9. Since the bars are drawn at a 50% confidence level, 50% of them ought to include the mean value if many experiments are performed. 90% of the 90% confidence bars must reach the mean value if we do enough experiments. The 90% bars must be longer than the 50% bars because more of the 90% bars must reach the mean, 4-10. Case 1: Comparing a measured result to a "known" value. Sec if the known value is included within the 95% confidence interval computed as in Equation 4-7. Case 2: Comparing replicate measurements. Use Equations 4-8 and 4-9 if the two standard deviations are not significantly different from each other. Use Equations 4-8a and 4-9a if the standard deviations are significantly different. Case 3: Comparing individual differences. (Use Equations 4-10 and 4-11.) 4-11. ¥ = Olds, s = 0.034 (2.015)(0.034) 90% confidence: sz = 0.14 TG = lds # 0.028 (4.032)(0.034) 99% confidence: =0.14g + 6 7 Olde + 0.056 4-12, 99% confidence interval: ¥ + (1.527 83 to 1.528 03) 4-13. (a) dL = deciliter = 0.1 L = 100 mL (©) Featcutated = (0.053/0.043)? = 1.59 < Fiable = 6.26 (for 5 degrees of freedom in the numerator and 4 degrees of freedom in the denominator). Since Featculated < Fiable, We can use the following equations: /0.532(5) + 0.422(4) 6+5-2 114.57- 13.951 [6-5 . t= “O98, \Ga5 = 2-12 <2.262 (listed for 95% confidence and 9 degrees of freedom). ‘The results agree and the trainee should be released. 0.484 Spooled24 4-14, Chapter 4 Sample Method 1 __Method 2 dj dj-d @-d) A 0.0134 0.0135 -0.0001-+0.0006 3.6 x 107 B 0.0144 0.0156 0.0012 0.0005 2.5 x 107 Cc 00126 0.0137 -0.0011 0.0004 1.6 x 107 D = 00125 0.0137 -0.0012. 0.0005. 2.5.x 107 E 00137 0.0136 40.0008 64x 107 a = -0.00070 sum = 16.6 x 107 (dj - > 16.6 x 10-7 . aie = 64x 10-4 00070 t= 0.00064 5 = 2.43 < 2.776 (Student's t for 4 degrees of freedom) The difference is not significant. 4-15. In the following spreadsheet, we find fcalculated (Which is labeled t Stat in cell F10) is less than fabte (t Critical two-tail in cell F14). Therefore the difference between the methods is nor significant. x 3S (cmae|ap E LF g 7 [Paired tiest __ [Fest Paired Two Sample for Mears | z i ‘S| Sample | Method 1_ |" Method Varable 1 |Varable® af A 0.0184 |" 00136, Mean 0.01852) 0.01403] Sf 8 | ora | 0.0166 [Variance 6276-07| —787E-07| e[ co 0.0126 | 00137 | [Observations — 3 5 75 0.0125 | 00197 Pearson Corlation ‘o7i107a27| o|e (0.0137 | 00136 Hypothesized Mean Difference a 2 al [Calculated t Statistic in coll FIO = — less than critical in cell F14 P(T=t)one-tall “0.03600077 [Therfore, the ference between the Critical one-tall 2.13184649] frethods isnot significant. | [P(T=t) two-all (0.07200153) [Chcaltwo-tal [e7ressoee] For Method 1, we compute ¥} = 0.082 6052, s1 = 0.000 0134 For Method 2, % = 0.082 005, s2 = 0.000 129 ‘The two standard deviations differ by approximately a factor of 10. We should use the F test to compare the two standard deviations: Feateulated = 822/512 = (0.000 129)2/(0.000 0134)? = 92.7 Frabte = 6.26. Since Featculaed > Fiable, We use Equations 4-8a and 4-9a, The following spreadsheet shows that calculated = 11.3 and fable = 2.57. Tealculated > table, $0 the difference is significant at the 95% confidence level.Statistics 25 Paired t test t-Test: Two-Sample Assur Unequal Variances Method 1 [Method 2 Varlabie 1 Variable | 0.082607] 0.08183) [Mean 0.082605] 0.082005} (0.082621| 0.08186] __|Variance 1.8E-10| 1.67€-08} 0.082589] ~0.08205| [Observations 5 a (0.082617| 0.08206] |Hypothesized Mean Diference ol 0.082598) 0.08215| lal 5 (0.08208| —[t Stat 11.31371|= Fealculated = 11.3 { 'P(T Fiable (for 27 degrees of freedom in the numerator and 17 degrees of freedom in the denominator). Since Featculated >Ftable» We use the following equations: 2 Degrees of freedom = Ji /™ +5 /M)° (sia, (im y itl mtd (0.002 25*/28 + 0.000 98° /18)* = | ( (0.002 25°/28)? | (0.000 987/18)? 28+1 18+1 -2 = 40.9 = 41 Izy - Fl 10.095 65 - 0.086 861 Fealculated a ny + Bin, (0.002 257728 + 0.000 987/18 ~ 182 ‘This is much greater than ¢ for 41 degrees of freedom, which is ~2.02. The difference is significant. For indicators 2 and 3: Featcutated = (0.001 13/0.000 98)? = 1.33 < Frabte = 2.2 (for 28 degrees of freedom in the numerator and 17 degrees of freedom in the denominator). Since Fealculated < Fables We use the following equations: 2 2 151? (ny — 1) + 827 (ng— 1) Spooled = *\ men? 0.001 0758 lz - min fealeulaed = seg \fm +m = 1.39 <2.02 = difference is not significant.26 4-19. 4-20. 4-21. Chapter 4 30.021) + 29.821) Spooled = 3243: = 299 5: 4. [32-32 39-730 = 2-88. The table gives r for 60 degrees of freedom, 29: which is close to 62. The difference is significant at the 95 and 99% levels. % = 97.09, 5 = 1.66 ts (2.776)(1.66) fy = 91008 = 97.00 2.05 95% confidence interval: jz = Range = 94.94 to 99.05 The 95% confidence interval does not include the certified value of 94.6 ppm, so the difference is significant at the 95% confidence level. If we make one more measurement, the results are ¥ =96.5g, 5 = 1.80 (2.571)(1.80) 95% confidence interval: #1 = 96.5g°—— 7g = 96.54% 1.89 Range = 94.69 to 98.47 ‘The 95% confidence interval still does not include the certified value of 94.6 ppm, so the difference is still significant at the 95% confidence level. (a) Rainwater: Feealculated = (0008/0.005)? = 2.56 < Frable = 4.53 (for 4 degrees of freedom in the numerator and 6 degrees of freedom in the denominator). Since Featculated < Fiable, We use the following equations: (0,0052(6) + 0.0087(4) Spooled = 745-2 = 0.00637 0.069 - 0.063 . [7-5 Fealeulated = 0.00637 \ 745 = 1-61 < fable = 2.228. ‘The difference is not significant. Drinking water: F calculated = (0.008/0.007)2 = 1.31 < Fable = 6.39 (for 4 degrees of freedom in the numerator and 4 degrees of freedom in the denominator). Since Featculated < Fable, We use the following equations: [0.0072(4) + 0.008°(4) Spooled = aL = 0.00752 4 -0.078 ~ = 9.087 = 0.078 ar oe 4 ee = 1.g9 <2.306. The difference is not significant.Statistics a (b) Gas chromatography: .0052(6) + 0.0072(4) = 0.005gg Ts ays = 261 > 2.228. The difference is significant. ‘Spectrophotometry: (0082(4) + 0,0087(4) Spooled = = = 0.00800 0.087 - 0.063, [5-5 1 = O08 \/545 = 4.74>2.306. The difference is significant. 4-22, Q = (216 ~ 204)/(216 - 192) = 0.50 < 0.64, Retain 216. 4-23, Slope =~1.298 72 x 104 (£0.001 3190 x 104) = -1.299 (£0.01) x 104 256.695 (£323.57) = 3 (#3) x 102 4-24, Xi Yi ai at dq e 0 7 0 0 007143 _0,00510 2 2 4 4 0.21429 0.04592 3 3 9 9 0.14286 0.02041 sums: 5 6 3 rr) 0.07143 n Zeuyi) - Dx Dy nZoiyi)-En Ey 3x13-5x6 9 n X(x42) — (Ly)? 3x13-52 ~ 1 Le?) Yyi-Low) Ey 13x6-13%5 13 ne) — (ayy? 3x 13-52 = 14 = 092857 [XL ¢ me Le = \ (S48 - 026726 4 oe ns = o2sra6y | = 0.12371 2 g Le) 3 1 wy = 5 \| Sp = 0.26726) 73 = 0.25754 oO o 1 ek slope = 0.64+0.12 intercept = 0.93 + 0.26 0.642 86 b4-26, 4-21, Chapter 4 x o ToT. The 2] 30) 0400 S| 10.9} ‘4 | 20.0) -2.5936+05) TT] te s0s | 30.0) -3.8896+05; 6] 40.0) -5.196E+05| 2405 7 6 LINEST output > 96405 | mf--r2se7 216) 10| Sq} 13.1899967| | t1|__ F'[o.ss9960 a 56408, 2 7 | 13 |Highiight cells BS:CT1 -sE05 14] Type _| Cr ° 75] "=LINEST (62:56 AB:AG, TRUE, TRUE)" x 16 [Press CTAL+SHIFT+ENTER (on PC) 17 [Press COMMAND+RETURN (on Mao) _| 4 ‘We must measure how an analytical procedure responds to a known quantity of analyte (or a known quantity of a related compound) before the procedure can be used for an unknown, Therefore, we must be able to measure out the analyte (or a related compound) in pure form to use as a calibration standard.Statistics 29 4-28. Hopefully, the negative value is within experimental error of 0. If so, no detectable analyte is present. If the negative concentration is beyond experimental error, there is something wrong with your analysis. The same is true for a value above 100% of the theoretical maximum concentration of an analyte. Another possible way to get values below 0 or above 100% is if you extrapolated the calibration curve past the range covered by standards, and the curve is not linear. 4-29. Corrected absorbance = 0.264 - 0.095 = 0.169 Equation of line: 0.169 = 0.01630 x+0.0047 = x=10.1 ng 430 (a) x= FHQt3+4t5V4=35 FH (1434446 /4=35 Xa -¥) = (1 - 3.5)? + (3 - 3.5)? + (4 -3.5)2 + (6—3.5)2 = 13.0 -&. fit, 0-9 «> tal \PR nT 2 Sey 92 = 019612. fl 1, @58—35? — _ ag 10.615 381 \/1*4* (0.615 38)2 (13.0) ~ Answer: 2.09 + 0.3g (b) For k=4 replicate measurements, sy 11 (y= 5)2, $x tl \fe tnt 2 S09? 0.19612 . fl 1, _@58-357 __ 94 10.615 381 \/4*4* (0.615 38)2 (13.0) ~ Answer: 2.09 # 0.26 4-31, Mean absorbance = (0.265 + 0.269 + 0.272 + 0.258)/4 = 0.2669 Mean blank: (0.099 + 0.091 + 0.101 + 0.097)/4 = 0.0979 => Corrected absorbance = 0.2669 - 0.0979 = 0.1699 Cells B30 and B31of the spreadsheet show that there are 10.1 + 0.2 1g protein30 Chapter 4 ATs 6 [Least Squares Spreadsheet 035 qo Ta|mea 7 2 3 4 a + 3 y=0.0163x + 0.0047 6 a 03 i | 7 3 a 3 3 3 10 9) ne 11 io 12 ao io 18, 15] | g 02 14 15) z 15, 20) £ 16 20] 5 a7 20] ons te 19 INEST output 20, ial 0.07630] 0.00270) on 21 a] 0.00022] 0.00263) 22 F* [0.99785 0.00588]5, 25] i 2a SOUNT(BA17) ce 25. 26 27, Iteanys——| 0:6ies]oos = AVERAGEACIT) H [E(x - mean x)° =| 723.214|B26 = DEVSQ(B4:817) mf] Ii 25 Measured y= —[ “EB ca ee er oer Namborst protein a) retcate Ineasrorens 29 jot y (k) = 4 ‘30 [Derived x 10.082| - 31s 0.2045] (C22/B20)"SQRT ((1/B29)+(1/B24)+((B28-B25)"2)/(B20°2"B26))Statistics 31 4-32, a a E E a a 7 Teast Squares Spreadsheet i 2 — { 3 Nemo ly a 7s 5 ea a73] 6 a 7 0.245 isa] | 3 0.486 3875 = of oar 812.5) E 0 1.921 1671.9 3 1 & 12 UNEST ouput ia ee cs ‘3 in| 059. 13]-22.088715 14 ‘Sal 10.6422] _6.9674]55 8 F*[_ 0.9909) 16 0527]s, 7[si7 = COUNTIBEETO) Saran te |Mean y= 45016, 818 = AVERAGE|C4:C10) 19 [2(.- mean x)" =| 2.87757]B19 = DEVSa(B4:810) aan aaaes 20 — 2i [Measured y= [12S fnput [ Number of replicate measurements zaloty (k= fioput 23 [Derived x Tawa B25 = WCBS - 24 ]s.= 0.0137]824 = (C1S1B13y'SORT((W/820).( 1817) +(B2t-Btey2V(B19'2°819) 4-33. (b) Corrected signal = 154,0-9.0 = 145.0 (©) Cells B23 and B24 give [CH4] = 0.192 (40.014) vol% (a), (b) Measurements are given in column C of the spreadsheet. (c) The answer in cells B40 and B41 is x = 31.9 (40.2) »M32 Chapter 4 x Ts Cc D E F G H T 7 [least Squares Spreadsheet | — z * 3 [Asti (pid) Current [nA] 800 | FJ # 20] 319 = = TE 750 y= 15.125x + 18.917 S 20,319 | 7 20] “sit —] 700 T s [20of 37 650 | cl ai /emes zo 37] 70 30] ar € 600 e at so] ars] | £ | 72 eof aap | 880 E 13 = 30] “ara sz Ig 14 30ers |B 7 30 an I 8 aq 17 “9 400 4 7 20 “9 40) 350 4 20 ag 21 40] 300 ane 22 a 20 30 40 50 23 59 Saf a As(it) (ust) 3 39 28 sof 27 so 28 = 2a UNEST out 30 mmf 15.1250) tasta7jp | =} 34 Saf 0.1042] 3.8272) 2 F[_0.9990| 570525, 3 = 2a)a= 2alpaa= COUNTIBEBE| ———|~ = 35 Neen y= Ea) sAGE(C4:C27) ‘96 [E(x - mean x)? =| 65.714286| 30(84:827) 7 627)| | ‘38 Measured = [Sor ohroat C Number ot repicate measurements saoty «= efirout oe 20 [Dervedx | STB7STalea0 = (Bae.coo/Ea) | — — — 41 [s.= 0.2142|B41 = (C32/B30)"SORT ((1/839)+(1/834)+((B38-B35)"2)/(B30"2"B36)) 4-34. 0.350 = -1.17 x 104 x2 + 0.01858 x-0.0007 1.17 x 10-4 x2 ~ 0.018 58 x + 0.3507 = 0 40.018 58 +y/0.018 582 = 4 (1.17 x 10) (0.3507; 2 (1.17 x 10-4) Correct answer is 21.9 ug = 137 or 219 yg 4-35. (a) The logarithmic graph spreads out the data and is linear over the entire range.Statistics 33 Current (nA) 4-36. 6000 5000 | Linear plot 4000 000 = gz 2000 1000 y= 17.063x + 32.183, ecco of © 100-200 300400 ae p-Nitrophenol (ig/ml) tog (ug/ml) (b) log (current, nA) = 0,969 2 log (concentration, g/mL) + 1.339 ©) log (99.9) = 0.9692 log (X] + 1.339 => log [X]=0.6816 => [X]=4.80 pg/mL For 8 degrees of freedom, t997% = 1.860 and t999% 90% confidence interval: 15.22 (41.860 x 0.46) 99% confidence interval: 15.22 (43.355 x 0.46) 355. 5.2 £0.86 4g S24 1sug5-1. 5-2. 5-3. 5-4. CHAPTER 5 QUALITY ASSURANCE AND CALIBRATION METHODS Get the right data: Measure what is relevant to the question at hand. Get the data right: Sampling and analytical procedures must be satisfactory to measure what we intend to measure, Keep the data right: Record keeping should document that samples were collected properly and data has demonstrated reliability. The three parts of quality assurance are defining use objectives, setting specifications, and assessing results, Use objectives: Question: Why do I want the data and results and how will L use them? Actions: Write use objectives. Specifications: Question: How good do the numbers have to be? Actions: Write specifications and pick an analytical method to meet the specifications. Consider requirements for sampling, precision, accuracy, selectivity, sensitivity, detection limit, robustness, and allowed rate of false results. Plan to employ blanks, fortification, calibration checks, quality control samples, and control charts. Write and follow standard operating procedures. Assessment. Question: Did I meet the specifications? Actions: Compare data and results with specifications, Document procedures and keep records suitable for meeting use objectives. Verify that the use objectives were met. Precision is demonstrated by the repeatability of analyses of replicate samples and replicate portions of the same sample. Accuracy is demonstrated by analyzing standard reference materials, by comparing results from different analytical methods, by fortification recovery, by standard additions, by calibration checks, blanks, and quality control samples (blind samples). Raw data are individual values of a measured quantity, such as peak areas from a chromatogram or volumes from a buret. Treated data are concentrations or amounts found by applying a calibration method to the raw data, Results, such as, the mean and standard deviation, are what we ultimately report after applying Statistics to treated data. 34Quality Assurance and Calibration Methods 35 5.5. 5-6. 5-8. 5-9, 5-10. A calibration check is an analysis of a solution formulated by the analyst to contain a known concentration of analyte. It is the analyst’s own check that, procedures and instruments are functioning correctly. A performance test sample is an analysis of a solution formulated by someone other than the analyst to contain a known concentration of analyte. It is a test to see if the analyst gets correct results when he or she does not know what the correct result should be. A blank is a sample intended to contain no analyte. A positive analytical response to the blank arises from analyte impurities reagents and equipment and from interference by other species. A method blank is taken through all steps ina chemical analysis. A reagent blank is the same as a method blank, but it has not been subjected to all sample preparation procedures. A field blank is similar to a method blank, but it has been taken into the field and exposed to the same environment as samples collected in the field and transported to the lab. Linear range is the analyte concentration interval over which the analytical signal is proportional to analyte concentration. Dynamic range is the concentration range over which there is a measurable (nonzero) response to analyte, even if itis not linear, Range is the analyte concentration interval over which an analytical ‘method has specified linearity, accuracy, and precision. A false positive is a conclusion that the concentration of analyte exceeds a certain limit when, in fact, the concentration is below the limit. A false negative is a conclusion that the concentration of analyte is below a certain limit when, in fact, the concentration is above the limit. ~1% of the area under the curve for blanks lies to the right of the detection limit. Therefore, ~1% of samples containing no analyte will give a signal above the detection limit. 50% of the area under the curve for samples containing analyte at the detection limit lies below (to the left) of the detection limit. Therefore 50% of samples containing analyte at the detection limit will be reported as not containing analyte at a level above the detection limit. A control chart tracks the performance of a process to see if it remains within expected bounds. Six indications that a process might be out of control are (1) a reading outside the action lines, (2) 2 out of 3 consecutive readings between the warning and action lines, (3) 7 consecutive measurements all above or all below36 Sell. 5-12. 5-13. 5-14, Chapter 5 the center line, (4) six consecutive measurements, all steadily increasing or all steadily decreasing, wherever they are located, (5) 14 consecutive points alternating up and down, regardless of where they are located, and (6) an obvious nonrandom pattern, Statement (c) is correct. The purpose of the analysis is to see if concentrations are in compliance with (ie., do not exceed) levels set by a certain rule. The instrument detection limit is obtained by replicate measurements of aliquots from one sample. The method detection limit is obtained by preparing and analyzing many independent samples. There is more variability in the latter procedure, so the method detection limit should be higher than the instrament detection limit, Robustness is the ability of an analytical method to be unaffected by small, deliberate changes in operating parameters. Ruggedness is a measure of precision. It is the variation observed when an assay is performed by different people on different instruments on different days in the same lab. Each analysis might incorporate independently prepared reagents and different lots of the same chromatography column from one manufacturer. When demonstrating ruggedness, the experimental conditions are intended to be the same in each analysis. When measuring robustness, conditions are intentionally varied by small amounts. Instrument precision, also called injection precision, is the reproducibility observed when the same quantity of one sample is repeatedly introduced into an instrument. Intra-assay precision is evaluated by analyzing aliquots of a homogeneous ‘material several times by one person on one day with the same equipment. Ruggedness, also called intermediate precision, is the variation observed when an assay is performed by different people on different instruments on different days in the same lab, Interlaboratory precision is the reproducibility observed when aliquots of the same sample are analyzed by different people in different laboratories at different times using equipment and reagents belonging to each lab. ‘The following graphs are taken from Excel. Error bars represent 1% or 10% of‘Quality Assurance and Calibration Methods 37 5-15. the y values for each point. Ideal, noiseless data for the charts were generated with the equation y = 26.4x + 1.37 to which 1% or 10% random Gaussian noise was added. 3000 Linear chart with 1% Gaussian noise 2500 Ty - 26.075x + 12.455 Pe 2000 FP = 0.9993 1500 1000 500 Concentration 0 20 40 60 80 100 3000 Linear chart with 10% Gaussian noise 2500 y= 23.936x + 141.27 FP = 0.9731 2000 1500 1000 500 : Concentration et 0 20 40 60 80 100 (a) For the fortification level of 22.2 ng/mL, the mean of the 5 values is 23.65 ng/mL and the standard deviation is 5.63 ng/mL. Precision = 100x 33 6g = 23.8%. .66 — 22.2, Accuracy = 100 x 286222 _ 6.6% For the fortification level of 88.2 ng/mL, the mean of the 5 values is 82.4 ng/mL and the standard deviation is 11.49 ng/mL.38 Chapter 5 ae 11.49 recision = 100 x $2.48 = 13.9%, Accuracy = 100 x Bg 882 6.5% For the fortification level of 314 ng/mL, the mean of the 5 values is 302.g ng/mL and the standard deviation is 23.5; ng/mL. 23.51 100x 395g = 7.8% Precision 02. 314 3 Accuracy = 100 x 3.6% 314 (b) Standard deviation of 10 samples: s = 28.2; mean blank: Ypiank = 45.0 Signal detection limit = yptank +38 = 45.9 + (3)(28.2) = 129.6 _ — 828.2) = 175% 108 Me 10)(28. Lower limit of quantitation = je =. =1.6x10-7M 3s Concentration detection limit = 7 48x 108M 5-16. (a) 1 wt% = C=0.01: CV(%) = 2(1-0.510g0.01) = 22 = 4% If C= 1012, CV(%) = 27 = 128% (b) If class CV is 50% of the value given by the Horwitz curve, it would be 0.5 x 2(1-0510g0.1) = 1.4% 5-17. “ LL. 7 a 5 % z 7_|C (a analyielg) _|Horwhtz CVs) 5° | 2 1,00E-05| __11.3137085| 2 Spiramycin | 1,00E-04| | 7 | 00€-03) — sasea5eD09 i St tone : 6 : 7 |B2 = 2ATO LOGI) 5 Sample points on 3° Horwitz curve tee EOF 1803 BOR €(g analytelg sample) 5-18. Mean = 0.383 g/L and standard deviation = 0.0214 g/L 0.383 ng/L % recovery = Gap ua = a0 gi * 100 = 96%Quality Assurance and Calibration Methods 39 5-19, 5-20. 5-21, ‘The measurements are already expressed in concentration units. The concentration detection limit is 3 times the standard deviation = 3(0.0214 g/L) = 0.064 ng/L ‘The low concentration of Ni-EDTA has a standard deviation of 28.2 counts for 10 measurements. The detection limit is estimated to be al = Yolunk +38 = 45 +3(28.2) = 129.6 counts To convert counts to molarity, we note that a 1.00 4M solution gave a net signal of 1797 — 45 = 1752 counts. The slope of the calibration curve is therefore estimated to be = —%sample=Yolank_ _ 1797-45 _ 1 75, gp counts ™ = Sample concentration = 1.00nM = ':/92* M ‘The minimum detectable concentration is (3)(28.2) counts 1.752 x 10° counts/M 3s 48x 108M For a concentration of 0.2 g/L, the relative standard deviation of 14.4% corresponds to (0.144)(0.2 g/L) = 0.028 8 ug/L. The detection limit is 3(0.028 8 g/L) = 0.086 ug/L. Here are the results for the other concentrations: Concentration Relative standard Concentration standard Detection (ng/L) deviation (%) deviation (ug/L) limit (g/L) 0.2 144 0.028 8 0.086 05 68 0.0340 0.102 1.0 32 0.0320 0.096 2.0 19 0.038 0 0.14 mean detection limit: 0.10 If an athlete tests positive for drugs, the test should be repeated with a second sample that was drawn at the same time as the first sample and preserved in an appropriate manner. If there is a 1% chance of a false positive in each test, the chances of observing a false positive twice in a row are 1% of 1% or 0.01%. Instead of falsely accusing 1% of innocent athletes, we would be falsely accusing 0.01% of innocent athletes.5-23, 5.24, Chapter 5 A small volume of standard will not change the sample matrix very much, 50 matrix effects remain nearly constant, If large, variable volumes of standard are used, the matrix is different in every mixture and the matrix effects will be different in every sample. Vi @ [Cu ]p = [Cu*]i 7, = 0.950 [Cu2*}, A 1.00 mL (©) [Slr = (Shy; = (100.0 ppm) C aacal = 1.00 ppm [Cu2+];, 0.262 © [00 ppm + 0.950[Cu (a) All solutions were made up to the same final volume. Therefore, we prepare a graph of signal versus concentration of added standard. The line in the graph was drawn by the method of least squares with the following spread- sheet, The x-intercept, 8.72 ppb, is the concentration of unknown in the 10- mL solution. In cell B27 of the spreadsheet, we find the standard deviation of the x-intercept to be 0.427 ppm. A reasonable answer is 8,72 + 0.43 ppb. y =8.196x +27.38 Signal = g g 2 in Added Sr (ng/mL) ‘The LINEST function used in cells B16-C18 was described in Section 4-7. Remember to highlight cells B16-C18 and press CONTROL+SHIFT+ENTER on a PC or COMMAND($)+RETURN on a Mac to execute LINEST.Quality Assurance and Calibration Methods 4 (b) © @ A 5 c D E 7 [Standard Addition Constant Volume Least- Squares Spreadsheet 2 a _ 4 x y _——_ onan 5 ‘Added Sr _ | 6 agit) ‘Signal 7 0.00| 28.000 8 2.50| 34.300] | | 9 ~ 5.00! 42.800] to} 7.50] 51.500] 1 70.00/ 58.600] 12 13 |B16:016 = LINEST(B7:B11,A7:A11, TRUE, TRUE) 14 T 15 LINEST output: 16 m| 3.1960] 27.3600b | 17 _ Sn] _0.0945| 0.5790}. | 18 FL o9e7s|_o7a7als, a) 3 20 fxcintercept = -bim: 21 22 |n= 3|Bo2 = COUNTIAT-ATI - 23 [Mean y= 43,040|B23 = AVERAGE(B7: 24 [B(x - mean x)" = 62.5|B24 = DEVSQ(A7:A11} 25 26 |Std deviation of = [27 fxiniercept Com _| 28 |B27 =(C18/ABS(B 16) SAAT (1/822) + B2S°2/(B10°2"B24) ‘The unknown solution has a volume of 10.0 mL with a Sr concentration of 8.72 ppb = 8.72 ng/mL. In 10.0 mL, there are (10 mL)(8.72 ng/mL.) = 87.2 ng. The solution was made from 0.750 mg of tooth enamel. The concentration of Sr in tooth enamel, in ppm, is mass of Sr ‘mass of enamel _ 872x109 g 0.750x10" g 6 Concentration (ppm) = x10 10° = 116 ppm 4.9%, which leads to a 4.9% uncertainty in the concentration of Sr in the tooth enamel. 0.049 x 116 ppm = 5.7 ppm. Final answer: 1166 ppm. ‘The relative uncertainty in the intercept is 100 x 0.43/8.7. ‘The value of Student's ¢ for n-2=5—2=3 degrees of freedom and 95% confidence is 3.182. We found that the standard deviation is 5.7 ppm. The42 5.25, 5-26. (b) (a) Chapter 5 95% confidence interval is + ts = (3.182)(5.7 ppm) = 18.1 ppm. Answer: 116 + 18 ppm. The intercept for tap water is -6.0 mL, corresponding to an addition of (6.0 mL)(0.152 ng/mL) = 0.91 ng Eu(MM). This much Eu(HID) is in 10.00 mL of tap water, so the concentration is 0.912 ng/10.00 mL. = 0.091 ng/mL. For pond water, the intercept of -14.6 mL corresponds to an addition of (14.6 mL)(15.2 ng/mL) = 2.22 x 102 ng/10.00 mL pond water = 22.2 ng/mL. Added standard Eu(IIl) gives a response of 3.03 units/ng for tap water and 0.0822 units/ng for pond water. The relative response is 3.03/0.0822 = 36.9 times greater in tap water than in pond water. There is probably a matrix effect in which something in pond water decreases the Eu(IlD) emission. By using standard addition, we measure the response in the actual sample matrix. Even though Eu(Iil) in pond water and tap water do not give equal signals, we measure the actual signal in each matrix and can therefore carry out accurate analyses. Data for the following graph are shown in the accompanying spreadsheet. The negative intercept is 0.140 M, which is the original concentration of analyte: [X] = 0.140 M. (If you had made a graph of /s-x versus [S]f, the intercept would have been [X]f= 0.070 M. You would have had to multiply ) [X]¢= by 50.00 mL/25.00 mL to find [X]j = 0.140 M.) T T y= 44.697x + 6.24 PT [| leet WVo y 015 010 005 0.00 005 010 015 020 025 x= [Sh'VIVoQuality Assurance and Calibration Methods 43 a 5 C D E [Standard Addition Variable Volume Least Squares Spreadsheet IV (mL) = Vs (mL) = x | = 50100] Naci Si) = Slandard_| axis function | \sex)= | y-axis function | added | Si'Vs/Vo signal ieey'Vvo_| Wo (Serum) (mi [_ 0} 3.13) 6.26| 0.1056] 5.40 70.80 _ o.2ti2| 7.89) 15.78 - 0.3168) 40.30] 0.4224) 12.48 1, TRUE, TRUE) LINEST output: “m]__44.6970) 6.2400) a Spl 0.5511 0.1425/55 a RL 0.9998) 0.18408, 20 pecintarcapt = -bin= a6] | a TI 2 { |n= 3 7-811) _| 23 |Mean y 15.68 \VERAGEV(ET:E11) 24|Z(i-meanx)*= | 0.1115136| EVSQ(C7:C11) _| 25] [ 26 [Sid deviation of 27 peintercept = = 26 [827 =(C16/ABS(B16) SOAT(1/B22) + B29°O(B16%2"B24)) (b). The x-intercept is computed in cell B20 and its uncertainty in cell B27. The relative uncertainty is (0.004 70)/(0.139 6) = 3.37%. This uncertainty is much larger than the relative uncertainties in volume measurement, so the uncertainty in the original concentration of Nat should be 3.37% A reasonable expression of [Nat] in the original serum is 0.140 (#3.37%) M = 0.140 (40.0047) M. 95% confidence interval = + ts = + (3.182)(0.0047 M) = + 0.015 M, where ¢ is taken for 5-2 =3 degrees of freedom. 5-27. Calculations are set out in the following spreadsheet. The concentration of unknown in cell B20 is 1.556 x 10°3M. The standard deviation in the intercept computed in cell B27 is 7.683 x 105M. Answer: 1.56 (+ 0.08) x 10°3 M. 95% confidence interval = + ts = + (3.182)(7.683 x 10°5 M) = + 2.4 x 10M, where 1 is taken for S — 2 = 3 degrees of freedom. Answer:1.56 (+ 0.24) x 10°3 M.44 Chapter 5 A B C D E FE [Standard Addition Variable Volume Least- Squares Spreadshest Io (mL) = Vs (miy= | x | - _ 50] volume. = (Si) = [standard Total volume if#x) = [y-axis function Ossijadded —_[V=Vo+Vs |Si'VsVo signal __|I(e+x)"VVo. _ 0.000 '50.000] | 1084! 1084. ~ 0.100 50.100] 0.001082} 7844] 1847-7| _ 0.200] 50.200) ‘o02t24] 2473 2482.9 10.900] 50.200] 0.003186 3266, 3285.6 ‘400| 0.400] 0.004248] —aot0| aaa. [Bi6:D18 = LINEST(F7:F11,07:D1 1, TRUE TRUE) LINEST output: ml 6.925E+05| _1.076E+03)b Sm|_1.339E+04) 3.482E+01]s, RF 0.9989 4.495E+01|5, bim = [7 ET ~ | a 20 |x-intercept = 21 _ 22\n 5|B22 = COUNT(87:B11) - = 23 [Mean y= (2548.4512 AVERAGE(F7:F11) 24 |E(xu - mean x)° = 15 DEVSQ(D7:D11) 25 26 |Std deviation of [_ 27 |xintercept= [| 1.683E-05] 7] 28 [B27 =(C18/ABS(B16)) SORT (1/822) + B29°2/(B16"2"B24) I 5000. y = 692473x + 1077.6 0,002 -0.001 0.000 0.001 0.002 0.003 0.004 0.008 xQuality Assurance and Calibration Methods 45 5-28. 5-29, 5-30. 5-31. Standard addition is appropriate when the sample matrix is unknown or complex and hard to duplicate, and unknown matrix effects are anticipated. An internal standard can be added to an unknown at the start of a procedure in which uncontrolled losses of sample will occur. The relative amounts of unknown and standard remain constant. The internal standard is excellent if instrument conditions vary from run to run. Variations affect the analyte and standard equally, so the relative signal remains constant. In chromatography the amount of sample injected into the instrument is very small and not very reproducible. However, the relative quantities of standard and analyte remain constant regardless of the sample size. Ax (fs) 3473 G 10222 @ py = Fis) > atom = F (qe) > F=0.168 0.847 mM. (b) [S] = A: As 5428 4431 © a 5 r(&) = ets (aaa) => [X]=6.16mM (@) The original concentration of [X] was twice as great as the diluted concentration, so [X] = 12.3 mM. For the standard mixture: a (8) i = Fis) > Chloroform added to unknown = (10.2 x 106 1L)(1484 g/L) = 0.015 14g = 0.1263 mmol in 0.100 L = 1.263 mM For the unknown mixture: Ax (48) STyA (ta 7 Ex) = Fis)? px = 94126 (77.265 maj) = P= 0.909 mM iogat) [DDT] in unknown = (0.909 mM) (i mE} = 9.09 mM. Data in the following table are plotted in the accompanying graph. If the equation area of analyte signal ___ (concentration of analyte area of standard signal = / (concentration of standard) is obeyed, the graph should be a straight line going through the origin, which it is. The slope, 1.0757, is the response factor. Over the concentration ratio analyte/standard = 0.10 to 1.00, the standard deviation of the response factor in46 Chapter 5 the table is 0.068 = 6.2%. Sample Concentration ratio Area ratio F= CioHs/CioDg___CioHs/CioDg__area ratio/cone. ra 1 0.10 0.101 1.0127 2 0.50 0.573 1.1461 3 1.00 1.072 1.0724 mean = 1.0757 standard deviation 0.0668 relative standard deviation 0.0629 ‘Area ratio 00 02 04 06 08 10 Concentration ratio6-1. 6-2. 6-3. 6-5. 6-6. 6-7. 6-8. 6-9. 6-10. 6-11. CHAPTER 6 CHEMICAL EQUILIBRIUM Concentrations in an equilibrium constant are really dimensionless ratios of actual concentrations divided by standard state concentrations. Since standard states are 1M for solutes, 1 bar for gases and pure substances for solids and liquids, these are the units we must use. A solvent is approximated as a pure liquid, All concentrations in equilibrium constants are expressed as dimensionless ratios of actual concentrations divided by standard-state concentrations. Predictions based on free energy or Le Chatelier's principle tell us which way a reaction will go (thermodynamics), but not how long it will take (kinetics). A. reaction could be over instantly or it could take forever. (@) K=W[Agt? PO} ] (b) K=Pco§/ Po!$? 3.6 x 108 Torr bars 3 (26x10 Tor. | 4), bar) Pi G5 Toratm * 1-013 iz) = = 12x 1010 P2[B] (28x 103 Pal a A 105 Parbar } (1-2 102M) HOBr + OCI = HOC] + OBr” Ky = 1/15 HoclL = Ht + OCr ky = 300x108 HOBr SH + OB -K=K,K, = 20x10 (a) Decrease (b) give off (c) negative K = ¢-(59.0 x 103 J/mol/(8.314 472 (K-mol)}298.15 K) = 5 x 10-11 (a) Right (b) right (c) neither (4) right (e) smaller (@) K= Py9 = eAGIRT = e(AH ~ TAS RT = e-{{(63.11 x 103 mol) — (298.15K)(148 J K-} mol-1)y(8.314 J K-! mot-!)(298.15 K)} = 4.7.x 104 bar (b) Puyo = 1 = eAH-TAS'YRT = AI TAS” must be zero a at AH’ -TAS’ = 0 > T= as (a) Let’s designate the equilibrium constant at temperature 7) as Ky and the equilibrium constant at temperature T as Ko. = 426K = 153°C 4748 6-12, 6-13, Chapter 6 Ky = e-AGURT, = (AM —TAS'YRT) = ¢-AH'IRT) « @AS'IR Similarly, Ka = e~AH™/RT2 « @ASIR K “ Dividing Kj by Kp gives & = e{AH'IR (UT, - 72) Putting in Ky = 1.479 x 10° at Ty = 278.15 K and Ky = 1.570 x 10° at Tp = 283.15 K gives AH” = +7.82 kJ / mol. (b) K = e~AH'IRT + gAS'IR A graph of In K vs 1/T will have a slope of -AH"/R (@) Q 48.0 Pa 7 1370 Pa } 3310 Pa 105 Pa/bar, / 105 Pa/bar \105 Pa/bar = 508x104 < K The reaction will go to the right. Note that it was not necessary to convert Pa to atm, since the units cancel. (b) Hp + Bro = 2HBr Initial pressure: 1370 3310 48.0 Final pressure: 1370-x 3310-x 48.0+2x Note that 2x Pa of HBr are formed when x Pa of Hz are consumed. 48.0 + 2x)? (1370-9 310-%) Puig = 1366 Pa, Ppry =3306Pa, Pup, = 57.0Pa = 172x104 > x=4,50Pa (©) Neither, since Q is unchanged. (@) HBr will be formed, since AH’ is positive. ‘The concentration of MTBE in the solution is 100 g/mL = 100 mg/L. The molarity is [(MTBE] = eoeor 13g x 103M. The pressure in the gas phase is P = [MTBE]/Kp = (1.134 x 10-3 M)/(1.71 M/bar) = 0.663 mbar.Chemical Equilibrium 49 6-14, 6-15. 6-16. 6-17. 6-18. 6-19. 6-20, [Cu*IBr] = Kep [Cur]f0.10] = 5x 109 = [Cut}=5x 108M [Ag*}4Fe(CN)$] = Kop [10x 10°6]4[Fe(CN)$} = 85x04 > [Fe(CN)$] =8.5x 1021M=8.5 2M If we let x= [Cu2#], then [SO%] = 4x. K = [Cu%J$ [OH] [S04] = (94 (1.0 x 10°96 dx) =2.3 x 109 => x= [Cu] = 3.9x107M (a) (Zn2+]2[Fe(CNY$] = (0.000 10)2[Fe(CNY$] = 2.1 x 10-16 => [Fe(CN)$] = 2.1x 108M (b) [Zn2+]2[Fe(CN)$] = (5.0 x 10°7)2[Fe(CN)$] = 2.1 x 10-16 => [Fe(CN)E] = 84x 104M BX» coprecipitates with AX3. This means that some BX; is trapped in the AX3 during precipitation of AX, For CaSO4, Ksp = 2.4 x 10°5. For AgoSOg, Ksp = 1.5 x 10°, Removing 99% of the Ca? reduces [Ca?*] to 0.000500 M. The concentration of S07 in equilibrium with 0.000 500 M Ca?* is 2.4 x 10°5/0,000 500 = This much SO, will precipitate AgaSOq, because Q = [Agt] [80%] (0.0300)? (0.048) = 4.3 x 10°5 > Kgp. The separation is not feasible. When Agt first precipitates, [S04] = 1.5 x 10°5/(0.0300)2 = 1.67 x 102 M. [Ca2*] = 2.4 x 10°5/1.67 x 102 =0.0014M. 97% of the Ca2+ has precipitated. BaCrOq(s) = Balt + CrOF Kp = 2.1 x 10-10 AgyCrO,(s) = 2Agt + CrO% Kop = 1.2.x 10-12 The stoichiometries are not identical, so itis not clear that the salt with lower Kep will precipitate first. Let’s try each possibility. Suppose that BaCrOg precipitates first. The concentration of CrO% that will reduce Ba2* to 0.1% of its initial concentration is [Ba2*][CrOZ] = [1.0 x 10-5][CrOF] = 2.1 x 10-10 = [CrO3] = 2.1x 105M Will this much chromate precipitate 0.010 M Ag*? We test by evaluating the reaction quotient for AgoCrO4:50 6-21. 6-22. 6-23, 6-24, 6-25. Chapter 6 Q = [Agt?{Cr04] = (0.010)22.1 « 105) = 2.1 x 109 > Ky for AgaCrOg. Since Q> Kep for AgoCrO4, Ag* will precipitate. Let’s try the reverse calculation. If AgoCrO4 precipitates first, the concentration of CrOF that will reduce Ag* to 1.0 x 105M is [Ag*}°[CrO3] = [1.0 x 10°5}2{CrO%] = 1.2 x 10-12 = [CO] = 0.012M This concentration of CrO% exceeds the concentration required to precipitate 99.90% of Ba?*. Neither Ag* nor Ba?* can be 99.90% precipitated without precipitating the other ion. Salt Kp AgCl 1.8 x 10-10 AgBr 5.0 x 10-13 5.0 x 10-12 Agi 8.3 x 10-17 8.3 x 10-16 AgCrO, 1.2 10-12 3.5 x 106 I requires the lowest concentration of Ag* to begin precipitating, so T- precipitates first. The order of precipitation is: I before Br before CI" before CrO%¢) At low I’ concentration, [Pb2*] decreases with increasing [I] because of the reaction Pb2+ + 217 — Pblp(s). Concentrations of other Pb?+-I’ species are negligible. At high I concentration, complex ions form by reactions such as Pbia(s) + T > Poi. (@ BF; (b) AsFs SnCl ot Bo => [SnClx(ag)] = Ba{Sn?*][C-}? = (12)(0.20)(0.20)? = 0.096 M [2n2*] = KepOHP =2.9 x 103M [ZnOH*] = By[Zn2*] (OH'] = B)Kgy/fOH'} = 2.3 « 105M [Zn(OH)3] = B3{Zn2*] [OH = B3Ksp [OH] = 6.9 x 10-7M (Zn(OH)%] = BalZn?*] [OH'}4 = BaKep [OH]? = 8.6 x 10°14 MChemical Equilibrium SI 6-26. 6-27. Net + OH = — NaOH(ag) Initial concentration: 1 1 0 Final concentration: 1-x x Toap = 02 = x S015 Mv x = 0.2-0.4x+0,2x2 0.222 - 1.4% +02 = 0 a ob xbaVP—4ac _ 142 ViP—40202) _ xe oA = HOD) = 6.85 or 0.15 x cannot be greater than I (the initial or formal concentration of NaOH), so the correct answer must be 0.15. That is, 15% of the sodium is in the form NaOH(aq). PIs) © PH + 2 Kop = [PREP = 7.9.x 109 + pot + 2F © pbig(ag) fo = (PbIa(ag)] / [POI = 1.4 « 103 PbI(s) = Pbio(ag) KK KepB2 = 1.1 * 10°5 = [Pbla(aq)) 6-28. ADE 5 E i g 1 [Keo = |Logft} |r] |(Ag*) TAgl(aq)} TAgle] _ TAgls) Z] asce17| 8) 1006-08) 4506-09) 5.88608] a 08e-T4] 252679] 3 = 77] 1.00E-07|4.50E-10 5.85E-09| 7.05E-13| 252-17) a] 1.306608) 6] —1.006-06 | Sas608| —_40se-12|—2.526-15 Aco 0) 1.00400] 4.50E-17} s.85E-09] 4.05E-06| 2.8203] 6 | 9.00810] (C2 De= [ease le2= | 7 [m= “Tionse —_|saszrce _[saswoarce _|snsaroecora _[saseozo2s _ | oY] se0eT3| | - 9 [B= llogfAg*] iloglAgl) logf llogiAgls] TO] 2.50E+14] =I 8.35) “823 “7359 =16.60} 11 [Ree = | [ -9.35| -8.23| 12.39) -16.60] iT] 76625 [035 8231.39] 14360] 13 |Kee- -16.35| “8.23 5.39] 2.60] Ta] 2.36200 [DW [E=—_F1>—_‘|610= 13 {LogT 0062) [Logi 6tE2) |Log 0%F2) ——~lLogt0%G2)52 Chapter 6 F T Z K + [aol Acer TAGahT [Adio 2 TIER 154635 “20E43 1.04608} a T1SE23 7 54E3T 2106-38] 3.30608 a T13E20 TB4Ea7) 2A0ESS B.80ES Ss) SE02 7.54 2.10E-03 231E02 [Fee - Rae TT 7_|sastoroe"c2Ns lsasianescas [DasEaFaG2sHaa.32 3 9 [lostAgh oat Agctl ~_ [leatAgsted ToOTAS oad — “42.68 7.99) “37.68 8.20) 32.68) 823] 2.68 “1.64 lite id= «KIO 15 |Looto(rey Log 02) [Lootorwe}__—__fuoato(K2y log(concentration) 6-29. Lewis acids and bases are electron pair acceptors and donors, respectively: F3B + :O(CH3)) > F3B- O(CH3)) Lewis Lewis acid base coe Bronsted acids and bases are proton donors and acceptors, respectively: HS + Ox > Or + HS” Bronsted Bronsted acid base(Chemical Equilibrium 53 6-30. 6-31. 6-32, 6-33, 6-34, 6-35, 6-36. 6-37. 6-38, (a) An adduct (b) dative or coordinate covalent (©) conjugate (d) [H+] >[OH]; [OH] > [H+] Dissolved CO2 from the atmosphere lowers the pH by reacting with water to form carbonic acid. Water can be distilled under an inert atmosphere to exclude CO>, or most CO> can be removed by boiling the distilled water. ‘SO; in the atmosphere reacts with moisture to make H2SO3, which is a weak acid, H2S03 can be oxidized to H2SQq, which is a strong acid. There is no place for OH" to bond to (CHs)4N*. (@) HI (b) HO 2H2S0, = HSO4 + H3SOZ acid base (a) H30* 2,0 (a) HaN CH)CH)N Hy HN CHaCH2NH) (b) CgHsCO2H Ce6HsCOz (b) CsHsNH* CsHsN (a) (H*] = 0.010 M => pH = —log [H*] = 2.00 (b) [OH] = 0.035 M => [H*] = Kw / [OH] (©) [H*] = 0.030M => pH = 1.52 (d) [H+] = 3.0M = pH =-0.48 (©) [OH] = 0.010M = [H*] = 1.0x 102M = pH = 12.00 .86 x 10°13 M = pH = 12.54 (a) Ky = (H*] [OH] = 1.01 x 10-14 at 25°C x2 = 1.01 x 10°14 = x =[H*] = 1.005 x 10-7 M => pH =-log [H+] = 6.998 (b) At 100° C, pH = 6.13254 6-39. 6-40. 6-41. 6-42. 6-43. 6-44, 6-45. 6-46. 6-48. Chapter 6 Since [H+] [OH] = 1.0x 10-4, K =[H*]4 [OH ]4 = 1.0 x 1056 [La3+] [OH'P = Key =2 x 107! (OH = Kp / (0.010) => [OH] = 5.8 x 10-7 M=> pH =7.8 (a) At 25°C, Ky increases as temperature increases => endothermic (b) At 100°C, Ky increases as temperature increases => endothermic (©) At300°C, Ky decreases as temperature increases => exothermic See Table 6-2. RCOQH R3NH+X” Mt Weak acids: Carboxylic Ammonium Metal acids ‘ions fons ‘: RCO;M* R3N: 2! Weak bases: gine Carboxylate CkCCOzH = ClyCCOz+ Ht Orin = Opie oe Lait + H20 = LaOQH?+ + Ht © +H,0 >= Om + OW HOCH2CH)S’ + H20 = HOCH,CH)SH + OH Ky HCO; = Ht + COF Kp: HCO}+ Hj0 = HyCO3 + OH” « P ky — (a) H3NCH2CH2NH3 = H)NCH2CH2NH3 + H’ + Kg HyNCH)CHNH; = © HyNCHCH:NHp + Ht rs : (b) O2CCH2CO3+ H2O 2 HO2CCH2CO; + OH” Kt HO,CCH;CO}+ HO = HO;CCH;COpH + OFF (a). ©)(Chemical Equilibrium 55 6-49. CN’ + 1,0 = HCN + OH" Ky Ke 6-50. H;P0, = HPO% + Ht HC;0j+ HyO = HyC204 + OT Ky Ky = oy 3 a 8 651. Ka = KL 7.04 x 10° Ka = KEE 6.25% 104 Ku 13, Ks = RE 435% 10 6-52. Add the two reactions and multiply their equilibrium constants to get K = 29x 10°. 6-53. (a) Ca(OH), (3) = Ca?* + 20H x 2 x(2x)? = Key = 10519 => x = 12x 102M (b) Since some Ca?* reacts with OH to form CaOH*, the Ksp reaction will be drawn to the right, and the solubility of Ca(OH), will be greater than we would expect just on the basis of Kep. 6-54. Reversing the first reaction and then adding the four reactions gives Cad + CO2(g) + HoO(l) = CaCOx(s) + 2H* K=Ke0yKiK2/Kep K = (3.4.x 102)(4.5 x 10-7(4.7 x 10! )/(6.0 x 10-9) = 1.2 x 10-10 TP 8x 1072 10 [Ca2*]Pco, = 1Ca?*y10.10] = K = 12% 10 [Cat] = 2.7x103M = 0.22 9/2.00L 6-55. To see which direction the reaction must proceed, evaluate the reaction quotient: HO3P(Br}!O0H*1!2 [0.005 00}2f0.005 00}!f0.005 00}!2 2 [Bra(aq)}5 7 [0.005 00]5 = 1911044 < K(=1x 1019) Since Q < K, the reaction proceeds to the right to reach equilibrium. Lys) + 5Bra(aq)+6H,0 = 210; + 10Br + 12Ht Initial concentration excess 0.005 00 0.00500 0.00500 0.005 00 Final concentration excess 0.001 0-2.5x 0.005 04x 0.005 00+5x 0.005 0046x56 Chapter 6 The following spreadsheet is like the one in the text, but the signs of the x terms in column C have been changed because the reaction proceeds to the right, not to the left. We could have used the spreadsheet in the text with negative values of x. Solve for x by systematic guessing or with Excel GOAL SEEK. The initial guess for xx was 0.001 and the value found by GOAL SEEK is x = 0,001 995 61. Final concentrations are given in column C. x B c D [Solving an Equation by Goat SEEK Initia Final Z | to.t= 0,008] 0.0069956| =B4+811 [e7]= | _ 0.005] o.o1497e1| -8545°B11 tH} = 0.005| 0.0169737| =B6+6B11 [Ero(aq 0.005] 0.000010] =B7-2.5°B11 Kea 1.00E-19| [C11 = $C$4A2"SC$S10°SC$EN1AIGCS7"5- s=l2l-1@]~]o]o[=Jels |] 6-56. No product is initially present, so the reaction must proceed to the right to reach equilibrium. The table shows initial and final concentrations. If [103] decreases by x, then [I] decreases by 5x; [H*] decreases by 6x, and [Ia(aq)] increases by 3x. 10; + SF + 6H «= lofaq) + 320 Initial concentration 0.001 00 0.001 00 0.001 00 ° Final concentration 0,001 00-x 0.0500-Sx 0.001 00~6x 2 In the following spreadsheet, initial concentrations are given in column B, x is, guessed in cell B11, and final concentrations are computed in cells C4:C7 by using initial concentrations and the value of x. In this particular problem, it is helpful to guess values of x until Q in cell C11 is within several orders of magnitude of K prior to using GOAL SEEK to obtain an exact answer. For example, guessing x 0.000 15 in cell B11 gives Q = 1.1 x 1035in cell C11. This value of x is sufficiently good to use GOAL SEEK to obtain an accurate value of x. Before using, GOAL SEEK, select OPTIONS from the TOOLS menu. Select Calculations and set Maximum change to 1e-24. To use GOAL SEEK, highlight cell C11 and select GOAL SEEK from the TOOLS menu. In the GOAL SEEK window, Set cell C11 ToChemical Equilibrium 37 value 3e48 By changing cell B11. When you click OK, GOAL SEEK finds x = 0,000 166 524 8 in cell B11, which gives Q = 2.997 x 1048 in cell C11. This answer is certainly good enough. However, if you run one more round of GOAL SEEK starting with x found from the first round in cell B11, you will get Q = 3.000 x 1048 in cell C11 Az a C D [Solving an Equation by GOAL SEEK initial Final 0.001] 8.335E-04| =B4-B11 0.001] 1.674E-04] =85-5°811 0.001] 8.509-07| =B6-6°811 EREEEPEEERE [etaq)) = 0} 4.996E-04| =3°B11 Kea = 3.006448] a a 0,0001665248] 3.0000E+45} csrrarg 1CSE75 S084) If you start with x too far from the correct value, you may not find solutions or you might find mathematically correct solutions that give negative concentrations for reactants or products. Clearly, you must look at the answers to be sure that they are physically sensible, not just mathematically correct.7-1. 72. 13. 1-4. 75. 78. CHAPTER7 LET THE TITRATIONS BEGIN Concentrations of reagents used in an analysis are determined cither by weighing cout supposedly pure primary standards or by reaction with such standards. If the standards are not pure, none of the concentrations will be correct. ‘The equivalence point occurs when the exact stoichiometric quantities of reagents have been mixed. ‘The end point, which comes near the equivalence point, is marked by a sudden change in a physical property brought about by the disappearance of a reactant or appearance of a product. Ina blank titration, the quantity of titrant required to reach the end point in the absence of analyte is measured. By subtracting this quantity from the amount of titrant needed in the presence of analyte, we reduce the systematic error. Ina direct titration, titrant reacts directly with analyte. In a back titration, a known excess of reagent that reacts with analyte is used. The excess is then measured with aa second titrant. Primary standards are purer than reagent-grade chemicals. The assay of a primary standard must be very close to the nominal value (such as 99.95-100.05%), whereas the assay on a reagent chemical might be only 99%. Primary standards must have very long shelf lives. Since a relatively large amount of acid might be required to dissolve a small amount of sample, we cannot tolerate even modest amounts of impurities in the acid for trace analysis. Otherwise, the quantity of impurity could be greater than quantity of analyte in the sample. 40.0 mL of 0.0400 M Hg2(NO3)2 = .60 mmol of Hg, which will require 3.20 os 3.20 mmol mmol of KI. This is contained in volume = 9399 mmol/mi. = 32-0 mL. 108.0 mL of 0.1650 M oxalic acid = 17.82 mmol, which requires 2mol MnO, 7 Smol HyC204, (17.82 mol H7C04) = 7.128 mmol of MnO4 7.128 mmol / (0.1650 mmol/L) = 43.20 mL of KMnO, ‘Another way to see this is to note that the reagents are both 0.1650 M. Therefore, Volume of MnO; = S(volume of oxalic acid) . 58Let the Titrations Begin 59 7-10. TAL 7-12. 7-13. 7-14, For the second part of the question, volume of oxalic acid = $(volume of MnOj) = 270.0 mL. 1.69 mg of NH3 = 0.0992 mmol of NH3. This will react with $(0.0992) = 0.149 mmol of OBr’. The molarity of OBr’ is 0.149 mmol/1.00 mL = 0.149 M. 0.3337 ‘mol sulfamic acid = 97 994 gma] = 34369 mmol 3.4369 mmol molarity of NaOH = ~375¢nq— = 1.1003 M HCI added to powder = (10.00 mL)(1.396 M) = 13.96 mmol NaOH required = (39.96 mL)(0.1004 M) = 4.012 mmol HCI consumed by carbonate = 13.96 ~ 4.012 = 9.94g mmol ‘mol CaCO3 = 3 mol HCI consumed = 4.974 mmol = 0.4978 g CaCO 0.497 g CaCOs Wi CaCOs = T5573 5 limestone * 100 = 92.0 wt% 5.00 mL of 0.0336 MHC! = 0.1680 mmol. 6.34 mL of 0.0100 M NaOH = 0.0634 mmol. HCl consumed by NH3 = 0.1680~0.0634 =0.1046 mmol = 1.465 mg of nitrogen. 256 UL of protein solution contains 9.702 mg protein. 1.465 mg of N/9.702 mg protein = 15.1 wi%. (a) Theoretical molarity = 3.214/158,034 = 0.02034 M. (b) 25.00 mL of 0.02034 M KMnO, = 0.5085 mmol. But two moles of MnOj react with five moles of H3AsO3, which comes from 3 moles of As,03. ‘The moles of As703 needed to react with 0.508 5 mmol of MnO; = (M)(5/2)(0.508 5) = 0.6356 mmol = 0.1257 g of As203. 5085 mmol KMnO4 _ x mmol KMnO4 "0.1257 g A803 = 0.1468.g AsyO3 =? * = 0.5939 mmol KMn0,j in (29.98 ~ 0.03) = 29.95 mL = [KMnOy] = 0.019 83 M. FM of NaCl = 58.443. FM of KBr = 119.002. 48.40 mL of 0.048 37 M Agt = 2.341 1 mmol. This must equal the mmol of (CI'+ Br). Let x = mass of NaCl and y =mass of KBr. x + y = 0.2386. x —y__ 38493 + 19.002 = 2.3411 x 103 mol moles of Cl’ moles of Br”60 715. 7-16. TAT. Chapter 7 Substituting x = 0.2386-y gives y 1,681 mmol of Br = 0.1343 g of Br 0.2000 g of KBr = 1.681 mmol of KBr = 6.28% of the sample. Let. x = mg of FeSO4-(NH4)2804°6H20 and (54.85 — x) = mg of FeCly-6H20. mumol of Ce = mmol FeSQ4:(NH4)2804-6H20 + mmol FeClz-6H20. ____xmg (54.85 — x) (13.39 mL)(0.01234 M) = 39973 mg/mmol * 234.34 mg/mmol => x= 40.01 mg FeSO4 (NH4)2S03- 6420. mass of FeCl 6Hj0 = 14.84 mg = 0.063 19 mmol = 4.48 mg Cl. 4.48 wt% Cl = 3a85 ma * 100 = 8.17%. 30.10 mL of Ni2* reacted with 39.35 mL of 0.01307 M EDTA. ‘Therefore, the Ni2* molarity is oy, — (39-35 mL)(0.013 07 mol/L) [N24] = 30.10 mL = 0.01709 M. 25.00 mL of Ni2* contains 0.427 2 mmol of Ni2+. 10.15 mL of EDTA = 0.1327 mmol of EDTA. The amount of Ni2+ which must have reacted with CN” was 0.4272- 0.1327 = 0.2945 mmol. The cyanide which reacted with Ni2* must have been (4)(0.294 5) = 1.178 mmol. [CN"] = 1.178 mmol/12.73 mL = 0.09254 M. (a) mol O2 = (2.9 x 106L)(2.2 x 104M) = 638 mol Reaction 1 requires 2 mol CH3OH for 3 mol O2, so the required CH3OH is (2/3)(638 mol) = 425 mol CH30H = 13.6 kg CH30H. ale = nau (b) 6NO3 + 2CH;OH -» 6NO} + 2CO2 + 4H20 6NO} + 3CH30H > 3N2 + 3COz + 3Hz0 + 60H volume of CH;0H net: 6NO3 + SCH30H —> 3N2 + SCOz + 7H20 + 60H" mol NO} = (2.9 x 106 L)(8.1 x 10°3M) = 2.35 x 104 mol Net reaction requires 5 mol CH3OH for 6 mol NO3, so the required CH3OH is (5/6)(2.35 x 104 mol) = 1.96 x 104 mol CH3OH = 627 kg CH30H. k volume of CH30H = cate = 793x102L (©) total volume required = 1.30 (17.2 L + 7.93 x 102L) = 1.05 x 10° LLet the Titrations Begin 61 7-18. 7-19. 7-20. 7-21. Prior to the equivalence point, all added Fe(III) binds to the protein to form a red colored complex whose absorbance is measured in the Figure. After the equivalence point, there are no more binding sites available on the protein. The slight increase in absorbance arises from the color of the iron reagent in the titrant. (a) 163 x 10°6 L of 1.43 x 103 M Fe(II) = 2.33 x 10-7 mol Fe(II) (b) 1.17 x 10-7 mol transferrin in 2.00 x 103L => 5.83 x 10°5 M transferrin ‘Theoretical equivalence point = mol Ga 0,003 57 g transferrin 2 thol transferrin \81 000 g transferrin/mol transferrin, mol Ga 0.006 64 = 133 pL Observed end point ~ intersection of lines taken from first 6 points and last 4 points 122 in the following graph = 12.2 UL, corresponding to 733 = 91.7% of 2 Galtransferrin = 1.83 Ga/transferrin. In the absence of oxalate, there is no evidence for specific binding of Ga to the protein, since the slope of the curve is small and does not change near 1 or 2 Ga/transferrin. ‘Theoretical end point = 13.3 pL y=0.00227x + 0.522 Intersection = Nee Absorbance y= 0.0405x + 0.0553 10 20 pL Gallium (i) T(excess) +Agt — Agl(s) [Agt] = Kep (for Agl) / [1] Gi) A stoichiometric quantity of Agt has been added that would be just equivalent toT,, if'no Cl were present. Instead, a tiny amount of AgC! precipitates and a slight amount of T remains in solution.62 7-22, 7-24, Chapter 7 (iii) Cr(excess) + Agt + AgCl(s) — [Agt] = Kep (for AgCl) / [CI] (iv) Virtually all - and Cl have precipitated. [Agt] = [Cl] => [Agt] =~/Ksp (for AgCl) (v) There is excess Ag* delivered from the buret. volume added past 2nd equivalence point (Ag*] = TAg*hicrant total volume At Ve, moles of Agt = moles of I” (Ve mL)(0.051 1 M) = (25.0 mL)(0.0823 M) = Ve = 40.26 mL 40.26 ~ 39. 25.00 When Vag+ = 39.00 mL, [] = Se 0.08230) (sees) = 1.006 x 103 M. [Ag*] = Kep/[I] = 8.3 x 10°14 M => pAgt = 13.08. When Vag+ = Ve, [Agt][T] = x2 =Kgp => x = [Agt] = 9.1 109M = pAgt = 8.04, When Vag+ = 44.30 mL, there is an excess of (44.30 — 40.26) = 4.04 mL of Agt. [Agt] - (ea tam) (0.051 10) = 2.98 x 103M => pAgt= 2.53. At the equivalence point, [Ag*}[F] = Kep => (x)(x) =8.3 x 10-17 = [Ag*] =9.1 x 10M. The concentration of Clin the titration solution is the initial concentration (0.0500 M) corrected for dilution from an 40.00 mL up to ~63.85 mL at the equivalence point: [cr] = (0.0500 m(902) = 0.0313M. Is the solubility of AgCl exceeded? The reaction quotient is Q = [Ag*][CI] = (9.1 x 109)(0.0313) = 2.8 x 10-10, which is greater than Kep for AgCl (1.8 x 101), Therefore, AgCI begins to precipitate before Agl finishes precipitating. If the concentration of CI: were about two times lower, AgCl would not precipitate prematurely. Moles of Ca2+ = moles of C,0% (Ve)(0.0257 M) = (25.00 mL) (0.0311 M) => Ve = 30.25 mL (a) The fraction of C20% remaining when 10,00 mL. of Ca?* have been added is (30.25- 10.00)/(30.25) = 0.669 4. [C,0%] = (0.669 4)(0.031 10M) a) = 0.01487M [Ca2+] = Kgp/[C204] = (1.3 x 10°8/(0.014 87) = 8.7 x 107 => pCa? = -log(8.7 x 10-7) = 6.06Let the Titrations Begin 63 7-25. 1-26. 7-21, (b) At the equivalence point, there are equal numbers of moles of Ca2* and C207 dissolved. Call each concentration x: [Ca2*] [C204] = (0%) = Kop = x 1.14 104M pCa?+ =-log(1.14 x 104)= 3.94 (©) [Ca?*] = (0.02570 M) eam = 0.00235M. — pCa?+ = 2.69 Equilibrium constants for ion pair formation: {10°" (x=cl 10° (X=Br) 10° (X=) [AgX(aq)] [Ag EX] Calling the ion pair formation constant Kf, we can write [AgX(aq)] = K;[Agt][X-]. But the product [Ag*][X°] is just Ksp. So, [AgX(ag)] = KeKyp. Putting in the values Kgp = 109-74 for AgCl, 10°12:30 for AgBr, and 10-16-08 for Agl gives {AgCl(aq)] = 1033110974 = 10643 M = 370M {AgBr(aq)] = 104-610-1230 = 107-7M = 20nM. [Agl(aq)] = 106610-16.08 = 10-9-5M = 0.32nM 82.67 mg__ mmol of BrCHCH9CH,CH2Cl = ie aon = 0.4822 mmol There will be 0.4822 mmol of CI’ and 0.4822 mmol of Br” liberated by reaction with CH30°Na*. 0.48: Agr required for Br° = 57egee= Nol = 18.76 mL. ‘The same amount of Ag* is required to react with CI’, so the second equivalence point is at 18.76 + 18.76 = 37.52 mL. Titration of 40.00 mL of 0.0502 M KI + 0.0500 M KCI with 0.0845 M AgNO3 0.050 2 M’ T + Agt — Agl(s) Ver = (40.00 mL) QaeM) = 23.76 mL, . . M CI +Agt— AgCl(s) Vez = (40.00 mL) (eas2 sooo Mm) = 47.43 mL ‘The figure gives Vez = 47.41 mL, which we will use as a more accurate value,64 7-28. Chapter 7 (@) 10.00 mL: A fraction of the I has reacted. = ( 36 ’ (0.0502 My = 0.0233M =“ —S Fraction Initial Ditton remaining concentration factor Kep(Agl) _ 8.3 x 10-17 = AoofAg) _ 831017 _ e [Ast] = ir) > 00233 = 357 10°15 M => pAg* = log [Agt] = 14.45 (b) 20.00 mL: A fraction of the I- has reacted. F 00) (0.0502 M) = 0.00530M 8.31017 [Ag*] = “9.00530 = (1.57* 104M = pAg* = 13.80 (©) 30.00 mL: I” has been consumed and a fraction of CI” has reacted, [cr] = @: 7S a) (0.0500 M) 0.0210 M. — Fraction Initial Dilation remaining concentration factor Kep(AgCl) _ 1.8 10-10 = KeolAsCh) _ a 5 tae] = “Tory = 0020 = 856% 109M = pAgt = 807 (@) [Ag*}[Cr] =x? =1.8 x 1010 = [Agt] = 1.3 105 = pAgt = 4.87 (©) 50.00 mL: There is excess Agt. 50.04 1.40 [Agt] = (0.0845 M) (25a) = 0.00243 M => pAgt = 2.61 — Tail Dihiion concentration factor Hg + 2CN™ > Hgo(CN)2(s)Kep = 5x 10-40 Agt + CN" > AgCNGs) Kp = 2.2 10-16 Kep for Hgo(CN)2 is much smaller than Kg for AgCN, so it looks like Hga(CN)2 will precipitate first. We will check that assumption soon, The equivalence point occurs at 20.00 mL. The second equivalence point is at 30.00 mL. At 5.00, 10.00, 15.00 and 19.90 mL, there is excess, unreacted Hg". 20. . At 5.00 mL, [Hg%'] = ( ST ) 0.1000 w0(sa9-238) = 0.05000 M