Solutions Manual for Quantitative Chemical Analysis Sixth Edition DANIEL C. HARRIS W. H, Freeman and Company New YorkISBN: 0-7167-4984-X (EAN: 9780716749844) © 2003 by W.H. Freeman and Company. All rights reserved. No part of this book maybe reproduced by any mechanical, photographic, or electronic process, or in the form of a phonographic recording, nor may it be stored in a retrieval system, transmitted, or otherwise copied for public or private use without permission from the publisher. Printed in the United States of America Fifth printing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 Chapter 29 The Analytical Process Measurements Tools of the Trade Experimental Error Statistics and Spreadsheets Calibration Methods Chemical Equilibrium Let the Titrations Begin Activity Systematic Treatment of Equilibrium Monoprotic Acid-Base Equilibria Polyprotic Acid-Base Equilibria Acid-Base Titrations Edta Titrations 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 Quality Assurance 12 18 23 35 43 52 59 70 7B 90 114 126 138 149 160 168 173 184 190 195 209 221 229 238 250 257 2600-1. 0-3. 0-4. 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. Convert a general question into a specific one that can be answered by a chemical measurement. (2) Select the appropriate analytical procedure. (3) Obtain a representative sample. (4) Sample preparation: Convert the representative sample into a sample suitable for analysis. If necessary, concentrate the analyte and remove or mask interfering species. (5) Analysis: Measure the unknown concentration in replicate analyses. (©) Produce a clear report of results, including estimates of uncertainty. (7) 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) A homogeneous material has the same composition everywhere. In a heterogeneous material, the composition is not the same everywhere, (b) 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 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0-6. ‘Chapter 1 segments with the help of a table of random numbers. We are apparently observing interference by Mn2* in the I- 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 F found by method A. Method B is not subject to the same interference, so the concentration of I- 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.1.2. 13. 1-4, 15. 1-6. 1-7. CHAPTER 1 3 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 results. In general, retain many extra digits for intermediate answers and save your roundoff luntil 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 (@ mW = millliwatt, «= 103 watt (b) pm picometer = 10-12 meter (© kQ kiloohm = 103 ohm (@ uF = microfarad = — 10° farad (©) TI terajoule == —10!2 joule () ns nanosecond = —_ 10°? second (® fe - femtogram = — 10-15 gram (p) dPa = decipascal = — 10"! pascal (a) 100 fJ or 0.1 pI (@) 0.1 nm or 100 pm (b) 43.1728 nF (© 21TW (©) 299.79 THz or 0.299 79 PHz (©) 0.483 amol or 483 zmol . . Lbar__ (@) 19 mPa=19x103Pa, 19x 103 Pa x Tosh = 1.9 x 107 bar (b) T (K) = 273.15 + °C = 273.15 — 70 = 203 K 1 Seg a oe 1.1x108M = 112M 0.083 14 de x 203 Table 1-4 tells us that I horsepower = 745.700 W = 745.700 Jis. 100.0 horsepower = (100.0 -hersepower | \Benepoac) = 7.457 x 104 Jis. 7.457 x 108% z 4.184 5 | (028 i e184 ar ar (rt \s-e00s ) = 20.Mskg) (120 pean (0.453 655 ) go y7 cal x3600f = 6.416x 107.1.8. 1.9. 1-10. 1-11. 1-12. 1-13. Chapter 1 = 2.0 Wikg Similarly, 3.4 x 103 = => 3.0 Iskg) = 3.0 Whkg (b) The office worker's power output is et J_)lday )/_1k J 6 eat a a pt (22% 108 aay )(4184 ae ea )e 00% )e Lx 1022 = 1.1 102.W. The person consumes more energy than the 100 W light bulb. @ 9.0254 -m = 7 => x = 39.37 inches 0 (ss f[ohi St (214 ™) (3 son) 770 milefh (772 if you did not round off 0.214) 0.214 mile (©) (3.00 2(345 2) = 1.04x 103m = 1.04 km 1 inch (25) ( I mile (1.04 x 108 /( 5-280 tect) = 0.643 mile 0.0254 wi) 12 inch Bio 1 I (5.00 x 103 Ty! 055.0 ) (= s00s = 147% 1082 = Newton = force = massx acceleration = kg: 3) Joule = energy = force x distance = ke (2) m= ks ( m-s? ‘ey = mol KI __200gKI__ _ 200g KI molality = Eg solvent 0.0 W% KT = 7990 g solution = 800 g HO To find the grams of KI in 1 kg of H2O, we set up a proportion: 200gKI_ __x g KI - 800 2120 = 1000120 ** = But 250 g KI= 1.51 mol KI, so the molality is 1.51 m (093 wag)! 000 Ei) (535 ker?) (root me) (i) 0 (a) molarity = moles of solute / liter of solution 250 g KI ton year (b) molality = moles of solute / kilogram of solvent (©) density = grams of substance / milliliter of substance‘Measurements 5 1-14, 1-15. 1-16. 1-17. 1-18, 1-19, 1-20. 1-21, (@) 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 / iter of solution Acetic acid (CH3CO>H) is a weak electrolyte that is partially dissociated. When we dissolve 0.01 mol in a liter, the concentrations of CHyCO2H plus CH3CO} add to 0.01 M. The concentration of CHyCO2H alone is less than 0,01 M. 32.0 g / {(22.989 770 + 35.4527) g/mol] = 0.548 mol / 0.500 L = 1.10M 1548 mol NaCl (! 71 Sotto ) (0.100 -L-setutton”) = 0.171 mol CH30H (0.171 meH€H3OH) (worersbr) = 5.48.g 1 ppm 3.77 x 10-4 mol => 3.77 x 104M. Kr: 1.14 ppm => 1.14 Kr per L of air => 4.60 x 108M Xe: 87 ppb => 87nL Xe perLofair = 3.5x 109M a 61.83 285 = 6.18 gin 2 L volumetric flask > 2.00 © x 0.0500 Weigh out 2 x 0.0500 mol = 120. .100 mol = 6.18 g B(OH); and dissolve in 2.00 kg Moon'Veon = Mait'Vait (80 ").004) = (028 tT) Vai => Vai = 3.2L We need 1,00 4 «0.1052! = 0.10 mol NaOH = 4.0 g NaOH 4.0 -£ NaOH _ 8.9 g solution 0.50 F solution (@) Veon = Vain Mit = 1000 mL (som) = 55.6 mL (6) One liter of 98.0% HSO4 contains (18.0 mo1)(98.079 g/emol) = 1.77 x 108 g of HyS04. Since the solution contains 98.0 wi% HSOq, and the mass of HS04 per mL is 1.77 g, the mass of solution per milliliter (the density) is 11 gh, 0,980 g-HySOq /g solution = 1,80 g solution/mL 2.00 L of 0.169 M NaOH = 0.338 mol NaOH = 13.5 g NaOH1-33, 1-34, Chapter 1 _ _gsolution density = aE solution = _13.5-gNaOM 8 & = = 151s (16.7 mL solution) (0.534 ? solution) FM of Ba(NO3) = 261.34 4.35 g of solid with 23.2 wt % Ba(NO3)p contains (0.232)(4.35 g) = 1.01 g Ba(NO3)2 mol Ba2* 1.01 aI) — = 3,86 x 10-3 mol = 261.34 2 BatNO3)2/mol) mol H2SOq = mol Ba2+ = 3.86 x 10-3 mol volume of H2SO4 = 88655107 mol) = 1.29 mL 25.0 mL of 0.023 6 M Th contains (0.025 0 L)(0.0236 M) = 5.90 10-4 mol Th+* mol HF required for stoichiometric reaction = 4x mol Th# = 2.36 x 103 mol 50% excess = 1.50(2.36 x 103 mol) = 3.54 10-3 mol HF Required mass of pure HF = (3.54 x 10° mo1)(20.01 g/mol) = 0.0708 g ; (0.0708 -¢ HF-) _ Mass of 0.491 wt % HF solution = 79-5491 —g-HF7e solution) = 4482-3. 2-4, 2-5, 2-6. 2-7, 2-8. 2.9, 2-10. 2-11. CHAPTER 2 9 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. PbSiO3 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 zero when the substance being weighed has the same density as the weights used to calibrate the balance. 0.0012 g/mL (14.82 8) (1- “Raga = = 14.85 g m= 1 Sere gint .626 g/mL ‘The smallest correction will be for PbO, 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 g(1 OgimL = = 42391 g 1 _ 0:0012 g/mL ( - 636 yi) 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 ‘true mass x 100 = “35397 « 100 = 0.06%. (a) One mol of He (= 4.003 g) occupies a volume of Lar ner _ (1 mob) (0.083 14 FE) (293-15 K) sean va"P = T bar = 24. Density = 4.003 g/ 24.37 L = 0.164 g/L = 0.000 164 g/mL10 2-12. 2-13, 2-14, 2-15. 2-16. 2-17. 2-18. 2-19. 2-20, 2-21. 222. Chapter 2 ©) m = —— soo tg = 0823 g ( ~ dor EL ) (a) (0.42) (2330 Pa) = 979 Pa (b) Air density = (0.003 485)(94 000) = (0.001 318979) = 41 gp, = 0.0011 gn 0.0011 g/mL (© mass = 1,0000g] ——8-08/mL__ | _ j oo10g 7 0001 T gmk 1.00 g/mL 2 9 _ 10M) 9 1, 2 (200 x 109g) _ AF (2:3 «10 Z al 106 He)? TE ioem ed) = [90H ‘TD means "to deliver" and TC means "to contain.” Dissolve (0.2500 L)(0.1500 mol/L) = 0.037 50 mol of K2SOs 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 20 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. Phosphorus pentoxide 20.2144 g - 10.2634 g = 9.9510g. Using column 3 of Table 2-7 tells us that the true volume is (9.951 0 g)(1.002 9 mL/g) = 9.979 9 mL. Expansion = J/ag7 9475 = 1.0020608 ~ 0.2%, Densities were taken from Table 2-7. The 0.5000 M solution at 25° would be (0.5000 M) / (1.002) =0.4990M.Tools of the Trade u 2.23. 2-25. Using column 2 of Table 2-7, ‘mass in vacuum = (50.037 mL)(0.998 207 1 g/mL) = 49.947 g. Using column 3, mass in ait = TOLLE = 49,892 g. When the solution is cooled to 20° C, the concentration will be higher than the concentration at 24” C by a factor of =22%sit¥#t20°€ | Therefore, the concentration density at 24° C needed at 24° will be lower than the concentration at 20° C. 1,000 Mp (9:297 299.5 Je 0.9991M Desired concentration at 24°C = 0.998207 1 g/mL (using the quotient of densities from Table 2-7). ‘The true mass of KNO3 needed is (0.5000 L) (0.999 1 ) (101 103 i) 50.506 g. 0012 g/mL’ (50.506 8) 2.109 g/ml) _ 5 agg 1 _ 0.0012 g/ml: = 50.484 g ( — 8.0 g/mL ) A B c 1_|Graph of van Deemter Equation 2 3 Flow rate [Plate height) | 4 _|Constants: (mL/min)| (mm. | | 5 4 8.194) | 6 1.65| 6 6.092) 7 8 5.064! 8 25.8 10 4.466) 9 = 20 3.412 70] 0.0236) 30) q 41 = 40 12 - 50) q 13 60, | 14 70! 1 15| 80 ° seed 16 90) 0 20 40 60 80 100 || 17 100 Te leona: tC Flow rate (mL/min) 1 9 |C5 = SAS6+SAS8/B5+SAS10°B5 |12 31. 3-2. 3-3. 3-4, 3-5. 3-6. 3-7. 3-8. 3-10. 3-11. CHAPTER 3 EXPERIMENTAL ERROR @s (b) 4 (©) 3 (a) 1237 (b) 1.238 (©) 0.135 @) 24 (e) 2.00 (a) 0.217 (b) 0.216 (c) 0.217 (b) 1.18 (3 significant figures) (c) 0.71 (2 significant figures) (@ 371 (b) 10.7 (©) 40x 10! (a) 2.85 x 106 (e) 12.6251 (f) 60x 10-4 (g) 242 (a) BaCly = 137.327 + 2(35.452.7) = 208.232 (b) Cyl1404 = 6(12.010 7) + 4(1.007 94) + 4(15.999 4) = 140.093 5 (The 4th decimal place in the atomic mass of C has an uncertainty of +8 and the 4th decimal place of O has an uncertainty of 3. These uncertainties are large enough to make the 4th decimal place in the molecular mass of CgHs04 insignificant. The best answer is 140,094.) (a) 12.3 (b) 75.5 (c) 5.520 103 (d) 3.04 (© 304% 101 () 119 (@) 4.600 (h) 49x 107 All measurements have some uncertainty, so there is no way to know the true value. See Section 3-4. The apparent mass of product is 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 random error superimposed on the systematic error, because the mass of moisture in the undried, empty crucibles will vary from crucible to crucible. (@) 25.031 ml. is a systematic error. The pipet always delivers more than it is rated for. The number + 0.009 is the random error in the volume delivered. ‘The volume fluctuates around 25.031 by + 0.009 mL. (b) 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.Experimental Error 13 3-12. 3-13. 3-14. 3-15. (@) 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, (a) Carmen (b) Cynthia (c) 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), 3.123g (40.17%) (a) 6.2 (40.2) = 4.1 (40.1) 21 te e2=0.24+0.12 = e=0.22 Answer: 2.1 +0.2 (or 2.1 + 11%) (b) 9.43 (40.05) 9.43 (+0.53%) 20.016 (40.001) => 0.016 (46.25%) %e? = 0532 + 6.252 0.15088 (t%e) => Ne = 6.272 Relative uncertainty = 6.27%; Absolute uncertainty = 0.15088 x 0.0627 = 0.009 46; Answer: 0.151 £0,009 (or 0.151 + 6%) (©) The first term in brackets is the same as part (a), 80 we can rewrite the problem as 2.1 (40.224) + 9.43 (40.05) = 2.1 (410.7%) + 9.43 (40.53%) %e = Y10.72 + 0.532 = 10.7% Absolute uncertainty = 0.107 x 0.223 = 0.0239 Answer: 0.223 40.024 (411%) (@) The term in brackets is, 6.2 (40.2) x 103 e=V0.22+0.12 > ©=0.204 +4.1 (40.1) x 103 10.3 (40.224) x 10°3 = 10.3 x 103 (42.17%) 9.43 (40.53%) x 0.010 3 (42.17%) = 0.097 13 42.26% = 0.097 13 40.002 20 Answer: 0.097; + 0.0023 (+ 2.3%) (@) Uncertainty = 10.032 + 0.022 + 0.062 = 0.07 Answer: 10.18 (40.07) (40.7%) (b) 91.3 (41.0) x 40.3 (40.2)/21.1 (40.2) = 91.3 (41.10%) x 40.3 (40.50%)/21.1 (40.95%) % uncertainty = V1.10? + 0.502 + 0.95? = 1.54% Answer: 174 (43) (42%) (©) [4.97 (40.05) ~ 1.86 (0.01)1/21.1 (40.2)14 3-16. Chapter 3 = [3.11 (40.0510)\/21.1 (40.2) = [3.11 (41.64%)/21.1 (40.95%) = 0.147 (41.90%) = 0.147 (40.003) (42%) @ 2.0164 (40.0008) 1.233 40.002) +461 (40.01) 7.8594 V(0.000 8)2+(0.002)2+(0.01)2 = 0.0192 Answer: 7.86 (40.01)(40.1%) (©) 20164 (40.8) + 123.3 (40.2) + 46.1 (40.1) 2185.8 V0.8)? + (0.2)2+ @1P = 08 Answer: 2185.8 (40.8) (40.04%) ( Fory=x#, %ey = a%ex X= 3.144005 => %ex=(0.05/3.14) x 100 = 1.592% ey = 5 (1.592%) = 0.531% Answer: 1.4643 + 0.007 (40.53%) (g) For y=logx, ey = 0.43429 & x= 3.144005 = ey = 0.43429 0.006 915 0.05" $28) Answer: 0.4969 + 0.0069 (+ 1.39%) 0.001 3.1415 (1.75 x 104) V3-14T3 = 3.1 x 104 Answer: 1.77243 + 0.0003 (@) y = x12 = %ey = 3 (100 x 0.0175% 0011 . = = 4 (b) y = logx =9 ey = 0.43429 31415) = 152% 10 0 Answer: 0.497 14+ 0.000 Is (©) y = antilog x= 10% = ey = x2.3026 ex = (103-141 5)(2,302 6)(0.001 1) = 3.51 Answer: 1385 40.0035 x 103 (@) y = Inx = ey =fRH = 35x 104 Answer: 1.14479 +0.000 35 (©) Numerator of log term: y = x! =9 ey = 5 ote x 100) 2.88% 0.3225 + 2.88% 0.3225 + 2.88% 0.0511 £ 0.0009 = 9.0511+1.76%Experimental Error 15 3-17. 3-18. 3-19. 3-20. = 6.311 + 3.375% = 6311+ 0.213 = = fx 0.213) _ For y= log x, ey = 0.43429 = 0.43429 Bari) = 01s Answer: 0.809 +0.015 ‘The uncertainty in the 1-g weight is + 0,034 mg. The uncertainty in the sum of the 4 weights is ¥0.0102 + 0.0102 + 0.0102 + 0.0102 = + 0.020 mg. In this case it is more accurate to use the 4 weights rather than one. C: 12.0107 + 0.0008; H: 1.00794 + 0.00007; O: 15.9994 + 0.0003; N: 14.006 74 + 0.00007 +9C: — 9(12.0107 + 0.0008) 49H: — 9(1.007 94 + 0.00007) +60: — 6(15.9994 + 0.0003) 3N: — 3(14.006 74 + 0.00007) CoH9O6N3: 255.184 3+ Uncertainty = 0.007 2? + 0.000 63? + 0.001 8? + 0.000 212 = 0.007 45 Answer: 255.184 + 0.007 108.096 3 + 0.007 2 9.071 46 + 0.000 63 95.996 4 + 0.001 8 42.020 22 + 0.000 21 (a) Na = 22.989770 + 0.000 002 g/mol Cl = 35.4527 _+.0.0009_g/mol 58.442470 (2 x 10°6)2 + (9x 10-42 = 9x 10-4 58.442 5 + 0.0009 g/mol mol _ {2.634 (40.002)g] / [58.4425 (£0.00 9)g/mol} (b) molarity = “[™ = 0.100 00 (0.00008) L _ 2.634 (+0.076%) / [58.442 5 (40.001 5%) 0.10000 (+0.08%) relative error = (0.076%)? + (0.001 5%)? + (0.08%)? = 0.11% molarity = 0.4507 (40.000 5)M. 1 — 0.001 2(40,000 1) g/mL 0.997 299 5 g/mL16 Chapter 3 [1.0346 (40.019 3%)] | 1 m= 8.0 (46.25%) 1- 0.001 2 (+8.33%) 1.997 299 5 (40%) m= [1.0346 (40.019 3%)][1 — 0.000 150 (+10.4%)] [1 - 0.001 203 (+8.33%)] m= [1.034 6 (40.019 3%)] [1 — 0.000 150 (+0.000015 6)] [1 - 0.001 203 (40.000 100)} sm = {110346 (40.019 3%)] [0.999 8500 (£0.000015 6)] [0.998 797 (+0.000 100)] [1.0346 (40.019 3%)I [ [0.998 797 (40.010 0%)] 1.0357 (40.021 8%) = 1.0357 (40.0002) g m= _0.2774£0.001gg _ 0.2774 4 0.001g 3-21. mol Fe203 =—"T59 688 gimol = 159.688 ~ 159.688 = 1.7371 + 0.0113 mmol Fe203; mass of Fe = 2[1.7371 (40.0113) x 10-3 mol][55.845 g/mol] = 0.19492 + 0.00126 g (0.19492 + 0.00126 g)/12 = 16.168 + 0.105 mg = 16.2+0.1 mg mass of Fe per tablet 3-22. mol H+ = 2x mol NayCO3 I NagCOy = -0:9674 (40.0009) g _ __0.9674 (40.093% mol NaxCO3 = 795.988 (40.001) g/mol ~ T05.988 (40.000 94%) g/mol = 0,009 1274 (#0,093%) mol mol H+ = 2(0,009 1274 (£0.093%)) = 0.018 255 (40.093%) mol (Relative error is not affected by the multiplication by 2 because both mol H+ and uncertainty in mol H* are both multiplied by 2.) . 18.255 (£0.093%) mol _ 0.018255 (£0.093%) mol molarity of HCl =-9 99735 (0.00004) L_ ~~ 0.02735 (£0.146%) L = 0.66746 (40.173%) = 0.667 46 (0.001 155) .667 + 0.001 M 3-23. To find the uncertainty in co®, we use the function y = x* in Table 3-1, where x = co . The uncertainty in co3 is 0.000 000 33 Foey = a %ex = 3%5.431 020 36 and a= x 100= 823 x 10°5%Experimental Ertor 7 So co3 = (5.431 020 36 x 10-8 cm)3 = 1.601 932 796 0x 10-2 cm? with a relative uncertainty of 1.823 x 105%, 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. Spreadsheets are introduced in Chapter 4.) The value of Avogadro's number is computed as follows: msi 28.085 384 2 g/mol ‘A (pco/8 (2.329 031 9 glem’ x 1.601 932 7960 x 10°22 cm3)/8 = 6.022 136 936 1 x 1023 mol! The relative uncertainty in Avogadro's number is found from the relative uncertainties in msi, p, and co?. (There is no uncertainty in the number 8 atoms/unit cell.) percent uncertainty in msi = 100 (0.000 003 5/28.085 384 2) = 1.246 x 105% percent uncertainty in p = 100 (0,000 001 8/2.329 031 9) = 7.729 x 105% percent uncertainty in co? = 1.823 x 10°5% (calculated before) percent uncertainty in Na =\%emg;2 + Tey? + (%eug3)? = = VL246 x 10-5)2 + (7.729 x 10°5)? + (1.823 x 10-5)? = 8.038 x 10°5% The absolute uncertainty in Na is (8.038 x 10-5%)(6.022 136 936 1 x 1023/10 = 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 (40.000 004 8) x 1023 or 6.022 136 9 (48) x 102318 4-1, 4-3, 4-4, CHAPTER 4 STATISTICS AND SPREADSHEETS 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 pertains to precision, not accuracy. (a) wo corresponds to z=-I to z= +1. The area from z=0toz= +1 is 0.341 3. The area from z = 0 to z = ~1 is also 0.341 3. Total area ( = fraction of population) from z= —1 to z= +1 = 0.6826. x0.4773 = 0.9546 (b) 2=-2t0z=42 => area= (© z=0to z=41 => area=0.3413 (@ z=0t0z=05 = area=0.1915 (©) Area from z=-1 to z=0 is 0.3413. Area from z=~0.5 toz=0is 0.1915. Area from z=-1 toz=-0.5 is 0.3413-0.1915 =0.1498. (a) Mean =} (1.526 60 + 1.52974 + 1.52592 + 1.52731 + 1.528 94+ 1.528 04 + 1.52685 + 1.527 93) = 1.52767 (b) Standard deviatio (1.526 60 52767)? + +++ (1.52793 — 1.527672 0.001 26 (©) Variance = (0,001 26)? = 1.59 x 10-6 (a) 1000 hours corresponds to z = (1000 - 845.2)/94.2 = 1.643. To find the area from % to z= 1.643, we interpolate between z= 1.6 and z= 1.7. The area from to z= 1.6 in Table 4-1 is 0.4452 and the area from ¥ to z = 17is 0.4554. ‘Area between z= 1.6 and z = 1.643 1,643 ~ 1.600 = (F00=1'600 )oass 4-0.445 2) = 0.0044 — Fraction of ‘Area between interval between z= 1.6andz=1.7 0.1.6 and z= 1.7 z Area from i to z = 1.643 = (area from ¥ to z = 1.6 + area from z= 1.6 toz= 1.643) = 0.445 2 + 0.0044 = 0.449 6 Area beyond z = 1.643 is 0.5000 ~ 0.449 6 = 0.0504 (b) 800 to 845.2: z=-0.4798 => area = 0.1842Statistics and Spreadsheets 19 4-5. 4-7. 4-8. 49, 4-10. 4-11. 4-12. 845.2 to 900: z= 0.5817 => area = 0.2195 Total area from 800 to 900 = 0.4037 ‘The values 14.55 to 14.60 correspond to the range (z= 0.5047) to (z Interpolating in Table 4-1, the area between the two is 0,334 2 — 0.193 972.0). =0.1411 ‘Your curve should look like the one in Figure 4-1. Use the same spreadsheet as in the previous problem, but vary the standard deviation. Here are the results: g Number of light bulbs 600 800 1000 1200 Hours ‘A confidence interval is a region around the measured mean in which the true mean is likely to lie. 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 bbe longer than the 50% bars because more of the 90% bars must reach the mean. Case 1: Comparing a measured result to a "known" value. (Use 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.) 0.148, 5 = 0.034 90% confidence: j= 0.14g + 201500 = 0.14g £0.02 99% confidence: p= 0.14g + Cone) = 0.14g + 0.055 999% confidence interval: & + @207 “oe 91 ~ 40,0010 (1.527 83 to 1.528 03).20 Chapter 4 4-13. (a) dL = deciliter = 0.1 L = 100 mL, (b) Fealculated = (0.053/0.04)? = 1.59 Fiable = 2.2 (for 27 degrees of freedom in the numerator and 17 degrees of freedom in the denominator). Since Fealculated >Ftables We use the following equations: Deprees of freedoen = 2imy + 52/2)? Brees 0 meni, + een * n+l nigel a+r t 1841 (0.002 252/28 + 0.000 982/18)? "ee 002 252/28)2 (0,000 982/18) |? = 409=41 ly - al 10.095 65 - 0.086 861 Tealculated = Sd ETT TTT CTITS smnee is12iny + 522g -Y'0.002 257/28 + 0.000 987/18 = 18.2 This is much greater than f for 41 degrees of freedom, which is ~2.02. The difference js significant. For indicators 2 and 3: Fealculated = (0.001 13/0.000 98)? = 28 degrees of freedom in the numerator and 17 degrees of freedom in the denominator). Since Fealculated 2.306. Difference is significant. . 063 [5-5 545 Q = (216 ~ 204) / (216 - 192) = 0.50 < 0.64. Retain 216.5-1. 5-2. 5-3, CHAPTER 5 CALIBRATION METHODS Slope = -1.29872 x 104 (40.001 3190 x 104) Intercept = 256.695 (£323.57) = 3 (£3) x 10? 1.299 (40.001) x 104 23 Ai di AiYi Ei a 7 T v 0 0.07143 0.00510 2 2 4 4 0.21429 0.04592 3 3 9 9 0.14286 0.02041 sums: 5 6 ey “3 0 0.07143 Lay) —Zai Lyi _ 3x 13-5 x 6 2 = 061286 m=" Da) -(2x)2 3 x 13-52 Ley?) Ey, - Low) Bai _ 13x 6-13 x5 _ 13 _ bn EC?) = (ha)? 3x 13-52 14 ~ 099857 _4/L@) _ foo e a i 32 = 0.26726 7 sm = 5B = 026726) = 0.12371 Sb = Leb = (0.26726) ° 1 1 = 0.25754 o 1 2 slope = 0.64 40.12 intercept = 0.93 + 0.26 ‘Your spreadsheet should be similar to the one in Figure 5-9. Here is the graph: 55 50F 45 40 35 30F 25 2.0 1.5 1 2 3,4 5 624 Chapter 5 5-4. A B a) E F G H |x y. ‘Output from LINEST | | 2 3.0] -3.870E+04| Slope. st 3 40.0] -1.299E+05 = 4 20.0] -2.593E+05 5 30.0| -3.889E+05 6 40.0, -5.196E+05| 7 8 __|Highlight cells E3:F5 ‘9_| Type Press CTRL+SHIFT+ENTER (on PC) 70] “LINEST(B2:86,A2: 14 | 2 [Press COMMAND+RETURN (on Mac) 0 20 40 5-6. 5-7. 5-8 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. 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. Corrected absorbance = 0.264 — 0.095 = 0.169 Equation of line: 0.169 = 0.01630 x + 0.0047 => x= 10.1 ug 2.51 fo) x ote = ESS. 20 _ oy afi, 2m, Od xxi x = ini NE* D+ ~D ~ “D = 0196 IT, Ta = DeIs Vit (2.00? s+ $5 (b) Replace the 1/k inside the square root by + => 0% = 0.26Calibration Methods 25 5-9. (a) x B c D E F e T_| Least-Squares Spreadsheet for Data in Table 5-2 2 ‘3 [Numberof [x z x xa wa 4 [points (n) = ‘Of 0.0003 a Of 0.0050] 2.56-05, 5 14 ‘of 0.0003 0 (| 0.0050 | —2.58-05 6 (| 0.0007 0 (0 -0.0040 | —1.6-05 7 0.0857] 0.4285 25] 0.0005] —2.38-07 8 's|_0.0877[ 0.4385 25] 0.0015] 2.3E-06) 9 S| _0.0887] 0.4435 25] 0.0025] 6.3E-06 To To] 0.1827 1.827] 100] 0.0150] —2.38-04 ra 10] 0.1727] 1.727100] 0.0050] 2.5E-05 12 10| 0.1727 1.727] 100] 0.0050] — 2.56-05 13 15] 0.2457] 3.6855] 225] -0.0034] _1.28-05 14 15| 0.2477 3.7155] 225] 0.0014] 2.16-06 15 20] 0.3257| 6.514[ 400] 0.0049] 2.46.05 16 20] 0:3257[ —0.314{ 400] —-0.0049 | 2.4605, 17 20| 0.3307[ 6.614[ 400] 0.0001 | 5.5E-09 18 ‘Column Sums, 19 Esp aaesef 90s] as) ASE 0.00047 20 21 [b= wdde= ‘AID = SASHEIOBINBIO 22 TOIa5| 0.00588. ‘A24 = (DI9SA$5-BIO*CIDSAS2, 23 [m= sid devi) = 'A26 = (E19*C19-D19*BIOVSAS22 24] oores0[ 0.00027 B22 = SQRTIGIO/SASS-2) 25 [b= sid devib) = B24 = SBS22*SQRTISASS/SAS22) 26] 0.00s70] 0.00263 B26 = $BS22*SQRTEIS/SAS22) 27 F4 = C4-$AS214*B4 A826 28 29" | Finding uncertainty in x with Equation 5-14: 30 I 31 [Measured y= ‘Number of replicate values of y measured (K) = 32 0.169) a 33 | Derived x=. Uncertainty in x= 34 | 10.0820) 0.20448 35 36 [Derived xin coll A34=(AS2-A2GVA24 '37_[ Uncertainty in x in cell G34 = ($BS22/SA$24)*SQRT((1/SGS32)+ 38 'SA$34°2*SASS/SAS22+$ES19/SAS22-2"$ AS34° SBS 19/SA$22) (b) Average unknown = 0.2669; average blank = 0.0979 corrected absorbance = 0.2669 - 0.0979 = 0.1699 _, 0.1699 = 0.0047 _ * = O01639 = 10.08HE (©) In spreadsheet cell G34, we find the uncertainty in x to be 0.20448. A reasonable final answer is.x = 10.1 +0.2 ug26 5-10. Chapter 5 c D E F c a for Data in Table 5.2 [Measured [Corrected ss |e eo oi] 00} | __22.06]_ 4.9509] 47.5| 38.4] 2.3808] 0.004| _6.60)_4.4+01 95.6 86.5] 10.553] 0.015] 2.59] 63EH 193.8] 184.7] 45.2521 0.06| 6.15] 3.8E+01 387.5[ 378.4] 183. 0.236 21.91] 4.88402 812.5] 803.4] 780.1] 0.943] 18.44] 3.4600] 1671.9] 1662.8] 3194.2] 3.69[ 15.28] 2.36409] ——Column Sum: a7] _S1S42]_ 4216.4] 4.948) 7E-13]_ 1629.5 20.143] mn SASS*F12-BI2°B12, 369.135} (EI2*$AS5-B12*DI2VSASIS, b= (F12*D12-E12"B 12V$AS1S 'SQRT(HI2($AS5.2)) SBSI5*SQRT(SASS/SASIS) [B19 = $BSIS*SQRTIFIZSASIS) [Finding uncertainty in x with Equation 5-14: 24 [Measured y 4 Number of replicate values of y measured (0) = 25 ia qa 26 [Daca x= [Gncenainty mae 27-{ 0.19724 “oor 28 29 [Derived x in cell A27 =(A25-A19VA17_ 30 [Uncertainty in x in cell G27 = ($B$15/$A$17)*SQRT((1/$HS25)+ Ba $AS27°2"SASSISASISeSFS125AS15-2°SAS27*SDS Z8ASIS 2000 Cells A17 to B19 give = m= 869+ 11 1500 =069.1x-221 /4 = y b=-22.1489 F 1000, 4 B eo | 8 ° 09 05. 10 +15 ~ 20 CH, (vol %) (b) Corrected signal = 154.0-9.0 = 145.0 (©) Cells A27 and G27 give [CH4] = 0.192 (+0.014) vol%Calibration Methods 5-11. (a), (b) Measurements are given in column C of the spreadsheet. Teast Squares Spreadsheot for Data in Table 52 k= = [Namber of — [As(II) GaN] Current (MAY ee a points (= of 319] eaa0|—a00] ATT SHED 2 20 319 6380] 400] —-2.417] 5.8400] 20 5319] — e380] a00] 2.417] 5.8500] 20 ‘319 6380] 400] —-2.417] 5.8400] 20] 317] 6340] 400] 4.417] 2.06401 —t 2 317] 6340] 400 4.417] 2.06401 [ 30] 472] 14160] 900] 0.667] 4.4E-01) 30] 473] 14250] 900] 2.333] 5.4400] 30 473| 14190] 900] 0.333] 116-01] 30 472 14160] 900] 0.667] 44-01 20 7a 142201 900] 1.333] — 1.85200] 30 475] 14250] 900] 2.333] 5.4400] 0) 633] 25320 1600] 9.085] 8.35401 40 636] 25440] 1600] 12.085] 1.5402] 0 630] 25200] 1600] 6.083] 3.7401 0 630] 25200] 1600] 6.085] 3.7401 a0) 28] 25120] 1600 4.085] 1-701 <0} 632] 25280] 1600] 8.083] —6.5E01 Ea} TIs| 38750] 2500] -0.167] _ 2,8E-02] Ea} “772 — 38600] 2500] 3.167] 1.0E+0 Ei 772] 38600] 2500] 3.167] _1.OE+01 Ea 7764] 38200] 2500] 11.167] _1.2B+02 EN 7166] 38300] 2500] 9.167] _8.4+01| Ey rol 38500] 2500] 5.167] 2.7601 ‘Column Sums— — sao 13159] 505940] 32400] _-3E-14] 716.085 = sddev) = /AS5E29-B29*B29 Tap00.0} 5.7059 [A34 = (D29*$A$5-B29*C29/SAS32 n= sd dev(m) = [A36-= (E29%C29.D29*B29/SAS32 T1250] 0.1042] {QRT(G29/($AS5-2) sd devt) = 'SBS32*SQRT(SASS/SASID) Tesi] 3.8272] SBS32°SQRT(E29/SAS32) [E4 = C4-SAS34"B4-$AS36 Finding uncerainty nx with Equation 5-1 Measuredy = amber of replicate values ofy measured (2) 501 4 Derived x=, [Cneerainy inn = 31873 or Derived x in cell ASS = (A42-ASOVASA [Uncertainty in x in coll G44 = (SBS32/GAS34)*SQRT( USGS) 'SAS4472*S ASS/SAS32+SES29/SAS32-2*S AS44* $BS29/SAS32) 2728 5-12, 5-13. Current (nA) y= 15.125x + 18.917 m Current (nA) 0 10 2 30 40 60 Asilll) (uM) Chapter 5 = 15.12 (£0.10) b= 18.9 (43.8) (©) The answer in cells A44 and G44 is x = 31.9 (40.2) 1M 0.350 = -1.17 x 10-4 x2 + 0.018 58 x - 0.0007 1.17 x 10-4 x2 ~ 0.018 58 x +.0.3507 = 0 +0.018 58 +V0.018 58 4.17 x10") (0.3507) _ 137 or 21.9 ug 2(L.17 x 10-4) Correct answer is 21.9 ug (a) The logarithmic graph spreads out the data and is linear over the entire range. 6000 000 |. Linear plot 4000 3000 Jog (nA) 2000 1000 y = 17.063x + 32.183 0 100-200 300400 P-Nitrophenol (ug/mL) y= 0.969x + 1.839 log (ug/ml) (b) log (current, nA) = 0.969 2 log (concentration, pg/mL) + 1.339 (c) log (99.9) = 0.9692 log [X] + 1.339 => log [X]=0.6816 => [X]=4.80 ug/mLCalibration Methods 29 5-14. 5-15. 5-16. 5-17. 5-18. y Sx y Sx » 5x 1 0.506 3 0.363 5 0.416 15 0.458 35 0.356 5.5 0.458 2 0.416 4 0,363 6 0.506 25 0.384 45 0.384 For 8 degrees of freedom, tog = 1.860 and to9q, = 3.355. 90% confidence interval: 15.2, (41.860 x 0.4) = 15.27 + 0.86 ug 99% confidence interval: 15.2 (43.355 x 0.46) = 15.94 1.5 wg ‘A small volume of standard will not change the sample matrix very much, so 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. @ (cure = 1h FE = 0.950 [Cu2+}; Vj 1.00 mL ®) [Slr = [Shiyt = (100.0 ppm (ioo.0 mt) = 1.00 ppm 2+]; ).262 © [00 Fee ORE, * 0300 = [CuP*}i = 1.04 ppm (a) The intercept for tap water is ~6.0 mL, corresponding to an addition of (6.0 mL)(0.152 ng/mL) = 0.917 ng Eu(D). This much Bu(IM) is in 10.00 mL of tap water, so the concentration is 0.91 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.Chapter 5 (b) Added standard Eu(II) 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. We describe this observation as a matrix effect. Most likely, something in pond water decreases the Eu(II1) emission. By using standard addition, we measure the response to in the actual sample matrix. Even though Eu({Il) 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. 5-19, (a) Data for the graph are shown in the spreadsheet. The negative intercept of the ‘graph is 0.069 8 M. The original concentration of analyte is twice as great because 25.00 mL was diluted to 50.00 mL in each flask. The original concentration of Nat is therefore 0.140 M. T [Standard addition: Mix 2.64 M Nas with 25.00 mi serum 2 3 [WGoabGmt)= [Vs = NaCl [x-axis fonction [1H = 4 ‘SOfadded (mL) [Si* V/V total) [signal (mV) = (Sapa 0.000] 0.0000] 314] 6 2.64] 1.000] 0.0528! 5.40] 7_[Weerum (ml) =| 2.000] 0.1056] 7.89] 8 23] 3.000] 0.1584 10.30] 9 4.000] 02112 12.48] 10 L1_|C5= SASO*BSISASECalibration Methods 31 x B € D E E c T [rest squares spreadsheet for Siandard dation raph 2 3_[Nomber of fr ry i a _|a ea 4 fpoints (a ‘O.o000| 3.73 7.0000] 070700} 1.000] 3 0.0528] 5.40] 0.0028] —-0,0800} 6.400803 6 0.1056 7.89 0.0112] 0.0500] 2.500E-03] 7 [0.1584] 10,30 0.0251 0.1000] 0008-02] 3 o2i12 12.48 0.0446] -0/0800|6.400E-03 9 Column Sung | T0_fsums CHa] 392] 5.3856] 0.0836] 0.0000] 254° OH] 11 12 [p= __|sd dev) =| [Finding uncertainty in x-intercept Tor st 13 | 01393941 0.0920] ‘addition with Equation 5-17: 14 [n= sd dev(m) = 1s | aa697d 0.5511 “HGR 16 [b= sddew() =| 0.002350] 17-{ 3120 0.0713] 18 19 [Fa= CESASTS*BESASIT Bo [Gt = Fara] — 21 [Bi0= SUM@aBS 22 [AIS = SASS*E10.BIOBIO IBIa = SORTIGIOGASS-O) 23 [AIS = (DIO*SASS-BIO°CIOVSASIS B15 = $BS13*SQRTGASSISATI) Z4[AIT=(E10°C10-D10°BIOVSASIS: [BIT = SBS1S°SQRTEIOSASI3) 25 26 SASITSASIS 27 SBS13/(SAS1S*SQRTISASI3)) SORT GASS*SFSISN2- 28 | 2°SFSIS*SB510s5E510) 4 we sof z Sek Ber Intercept =-0.069 8 M 01 00 01 02 08 Concentration of added Nat, (Sk (M) (b) The x-intercept is computed in cell F15 and its uncertainty in cell F16. The relative uncertainty is (0.002 350)/(0.069 803) = 3.37%. This uncertainty is ‘much larger than the relative uncertainties in volume measurement, so the uncertainty in the original concentration of Na* should be 3.37%. A reasonable expression of [Na*] in the original serum is 0.140 (43.37%) M = 0.140 (20.005) M.32 Chapter 5 5-20. (a) Calculations to make the standard addition graph are set out in the spreadsheet: Standard addion/varible volume: Add 0331 MX to SO mi, unknown [Wo (mi) = [Vs= aided X [rans function [eex)= y-axis fonction SOfimLy [si*VVo | (countsimin) (Gx) V/Vo SiM)= 7.000|_— 0.000000] 108: 1084 On| ‘0.100 0.001062 1 1847. 0.200] 0.002124 247. 2482.51 10.300] 0.003186 326 3285. 0.400] 0.004248] 414042. ES = D5" SAS: BSVSASE E y= 6.925 E6 x+ 1078 2 Intercept = 0.001 556 \ -0.002 0.001 0.000 0.001 0.002 0.003 0,004 0.005 () concentration of standard X(M) (b) Cell F15 in the spreadsheet below shows that the original concentration of unknown is 0,001 556 M and the uncertainty in cell F16 is 0.000 077 M. A Teasonable way to express the results is 0.001 56+ 0.000 08 MCalibration Methods 33 5-21. 5-22. 2 3 fe Es eo la lao. 4 10-0000) 1084.0| 0.0000] 0.00005+00] 63600] 4.045601 5 (0.001062 1847.7] 1.9623] _1.1278E-06] 34.6500] 1.201E+03] 6 (0.002124) 2482.9] 5.2737] _4.5114E-06] _ -65.5600] 4.298E +03] 7 0.003186] 10.4679] 1.01518-05| 1.7300] 2.993E+00] 8 0.004248] '5.208E+02| 9 —_—_______¢ 10 Do1062o] —12742.3] 34.8747] 3.3835E-05] 0.0000] 6.063403] i 12 |D= std dew) = 13 | 5.639E-05} 4.496E+01] 14 std devim) = 15 | 69256405 1.3395 +04 16 [b= sid devi) = 17 | 1.0786+03) 3.482201 18 19 Fa = CA SASIS*BASASTI| 20 f 21 22 IRT GTONSASS-2)) 23 BS13*SORT ASI [A17 = (B10*C10-D10*B10YSASI3 et 25 26 |FIS = -SASITSASIS. 27_[F16 = (SBS13/(SA$1S*SQRTISASI3)*SQRT GASS*SFSIS™2- 2*SFS1S*SB$10+SES10) 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 _ (AS) , 3473 _ p/_10222 . @ X= F(s) > param = F(tr72 mM) > F= 01684 (b) [8] = 47 mM) (Typ mL) = 0847 mM Ax (As 5428 4431 - (d) The original concentration of [X] was twice as great as the diluted concentration, so [X] = 12.3 mM.34 5-23. 5-24. 5-25. Chapters For the standard mixture: Ax _ (As 10.1 pA _ (15.3 HA . ix] = F(s)) > [0.800 mM] = F (00 nN) = Fa0Al2g Chloroform added to unknown = (10.2 x 106 L) (1484 g/L) = 0.015 14g = 0.126g mmol in 0.100 L = 1.263 mM For the unknown mixture: A A 8.7 A 29.4 uA ® = F(§) => aya = 044126 (F365 mi) => [X] = 0.909 mM [DDT] in unknown = (0.909 mM) (io0'mt) = 9.09 mM Data in the table are plotted in the graph. If the equation area of analyte signal___, concentration of analyte area of standard signal ~ (Goncentration of standard is obeyed, the graph should be a straight line going through the origin, which it is. The slope, 1.076, is the response factor. Over the concentration ratio analyte/standard = 0.10 to 1.00, the standard deviation of the response factor in the table below is 0.068 = 6.3%. Sample Concentration ratio _ Area ratio CyoHg/Cy CioHs/Cy 1 0.10 0.101 1.01 2 0.50 0.573 1.15 3 1.00 1.072 1.07 19 Ty =1.0756x + 0.0084 08 2 = 06 g o4 02 0.0 0.0 02 04 06 08 1.0 Concentration ratio For 3 degrees of freedom, tog = 2.353 and t99% = 5.841. 90% confidence interval: 0.0423 (+2.353 x 0.0021) = 0.0423 + 0.0049 M 99% confidence interval: 0.0423 (£5.841 x 0.0021) = 0.04) + 0.012 M6-2, 6-3. 6-4, 6-6. 6-9, 6-10. 6-11. CHAPTER 6 35 CHEMICAL EQUILIBRIUM Concentrations in an equilibrium constant are really dimensionless ratios of actual concentrations divided by standard state concentrations. Since standard states are 1 M 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=IfAg*} [PO}] (6) K = Pco$/ Po}? x 104 Torr bar See 1.013 Be 0 in) 7 Beal Pe su = 12x10 "A CiosPamar F 2 x 10 M) HOBr + OCI * HOC! + OBr* HOC] = Ht + ocr HOBr = H* + OBr~ (a) Decrease (b) giveoff (©) negative K_ = e-(59.0 x 103 S/mol)/(8.314 472 J/(K-mol)\(298.15 K) = 5 x 1Q-11 (a) Right (b) right (©) neither (@) right ~—_(e) smaller (@) K= Pago = eAGIRT = e-(an"—1as°yRT = e-{[(63.11 x 103 H/mol) — (298.15K)(148 J/K/mol) /(8.314 472 J/K/mol)(298.15 K)} = 47x 10-4 bar (b) Puyo = 1 = e(AH'TAS'YRT > AH" —TAS* must be zero. AH’ - TAS’ = 0 > T 426 K = 153°C (0) Ky = e-AGIRT 2 @(AH'-T1AS°YRT] = @-AHRT « eASIR Ko = SHIRT « @ASIR Dividing Ky / K2 gives = e- AHIR (UIT ~ 1T2)36 6-12. 6-13, 6-14, 6-15. Chapter 6 =(L A)! pink ar =(r - ni) Ring Putting in Kj = 1.479 x 10°5 at Tj = 278.15 K and Ky = 1.570 x 10° at Tz = 283.15 K gives AH = +7.82 KI / mol. (b) K = c~AH'IRT + gASIR AH’ (1 AS ing =e (7) + yom x 6b A graph of In K vs 1/T will have a slope of ~AH’/R (©) 0 (765 pata) / (Zo Parr (108 Pabsr) = 5.08 x 10-4 < K The reaction will go to the right. Note that it was not necessary to convert Pa to atm, since the units cancel. ) Hy + Bry ? 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 H are consumed. (48.0 + 2x)? _ 4 _ W370 HEI0TH 772x104 > x=4.50Pa Pig = 1366 Pa, Ppr. =3306Pa, Pup, = 57.0 Pa (©) Neither, since @ is unchanged. (@) HBr will be formed, since AH" is positive. The concentration of MTBE in the solution is 100 wg/mL = 100 mg/L. The molarity is [MTBE] = 99° ee = 1.134 x 10-3 M. The pressure in the gas phase is P = [MTBEV/Kjy = (1.134 x 10°3 M)/(1.71 M/bar) = 0,663 mbar. (@) [Co IBr] = Ksp (@) @) = 5x10 = [Cut}=7.x 105M (b) (143.45 g/mol)(7.1 x 10-5 mol/L.)(0.100 L/100 mL) = 1.9 x 10°3 g/100 mL. (a) [AgtI*[Fe(CN)$] = Ksp 404 @) = 85x 1045 = x=5.06x1010M (b) (643.42 g/mol)(5.06 x 10-10 mol/L)(0.100 L) = 3.3 x 10°8 9/100 mL. (©) [Agt] = 4x= 2.02 x 109M = 2.18x 10-7 g/L = 2.18 x 10-7 mg/mL = 0.218 ng/mL = 0.22 ppb