Solutions Manual for Harris’ Quantitative Chemical Analysis Eighth Edition Daniel C. Harris Michelson Laboratory W. H. Freeman and Company New YorkISBN; 1-4292-3123-8 EAN: 978-1-4292-3123-7 © 2003, 2007, 2011 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 www.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 |4 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 The Analytical Process Measurements: Tools of the Trade Experimental Error Statistics Quality Assurance and Calibration Methods Chemical Equilibrium Activity and Systematic Treatment of Equilibrium Monoprotic Acid-Base Equilibria Polyprotic Acid-Base Equilibria Acid-Base Titrations EDTA Titrations Advanced Topies 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 Analysis, Precipitation Titratio and Combustion Analysis Sample Preparation 12 17 38 33 6t 7 82 97 126 142 175 189 202 217 230 238 251 260 269 284 298 3H 327 345 3600-1. CHAPTER O THE ANALYTICAL PROCE! Qualitative analysis finds out what is in a sample, Quantitative analysis measures how much is in a sample, Steps in a chemical analys (1) Formulate the question: Convert a general question into a specific one that can be answered by a chemical measurement. (2) Select the appropriate analytical procedure. (3) Obtain « representative sample, (4) Sample preparation: Convert the representative sample into a sarnple suitable for analysis. If necessary, concentrate the analyte and remove or mask interfering species. (5) Analysis: Measure the unknown concentration in replicate analyses. (6) 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. Ina not the same everywhere. heterogeneous material, the composition composition varies on a large (b)_ ina segregated heterogeneous material, the 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. (c) To sample a segregared heterogeneous material, we take representative amounts from each of the obviously different regions, In panel b in Box 0- nd 20% is C. To construet a 66% of the area has composition A, 14% is B,Chapier 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 Mn?* in the I- analysis by method A. The result of the F analysis is affected by the presence of Mn2*, The greater the concentration of Mn?* 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 Mn2*, 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. 1-2. 13. 1-5, CHAPTER 1 MEASUREMENTS A note from Dan: Don't worry if your numerical answers are slightly different from those in the Solutions Manual, You or \ may have rounded intermediate results, 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) Abbreviations above kilo are capitalized: M (mega, 106), G (giga, 10°), T (tera, 1012), P (peta, 1015), E (exa, 10!8), Z (zetta, 102!) and ¥ (yotta, 1024). (@ mW = milliwatt = 10-3 watt (b) pm == _—picometer «= 10! meter ()kQ = kiloohkm == 103 ohm (d) pF = microfarad = = 10°6 farad (e) TH = terajoule = 10!2 joule (9 ns = nanosecond = — 10? second (g) fe = femmtogram = 105 gram (h) dPa == ~—decipascal. «== ~—10"! pascal (a) 100 fF or 0.1 pd () 0.1 nm or 100 pm (b) 43.1728 nF (e) 21TW (c) 299.79 THz or 0.299 79 PHz (f) 0.483 amol or 483 zmol kg 5.4 Pe=5.4% 1015 ¢, x 1015 fx = 5.4% 1012 (a) 54Pg=54% 105g, 54x 1015 £ Tou g 5.4% 10! kg of C (b) The formula mass of CO2 is 12,0107 + 2(15.999 4) = 44.009 5 Dee #009 5 ke COs 54x 10? bee x15 O10 Tkge = 2.0 x 1013 kg CO2 (6) 2.0% 1013 Jef CO) x UE = 2.0 x 1010 tons of CO 1000 ba 2.010" tons =~ = 4 tons per person 5x10” people16. 18. Chapter 1 Table 1-4 tells us that 1 horsepower = 745.700 W = 745.700 J/s. 100.0 horsepower = (100. 0 ssn 745.700 24) = 1.457 «104 Ys. horsepower rast x08 2 1 7 £ x 36004 = 6416107 4.is4 2 cal 22 «108 af Vaasa \ sof (a } (a) BI) 7 e sen 2.0 Aske) kg (120 pou) 04596 2, pound = 2.0 Wikg kcal Similarly, 3.4 103 "> 3.0 W(skg) = 3.0 Wikg. lay (b) The office worker’s power output is [22 x wt a0) 22) = 1.1 10? ; = 11 102W The person’s power output is greater than that of the 100 W light bulb, y 5.00 x 10° 28 V/955.06— | 4) 247x108 = 147% Ww K 3600s s 1 foot 1 mile 7 (1000 2 SES 5280 foot) ~ 262137 km ) (asic 621 37 a “) ¢, miles >! gallon (©) The diesel engine produces gCO2 Li ) 359 2LO2 273 £002 || __IKM __| _ 359 (2 ei seo) 37 mile } mile kat gallon 23 g CO,/km, which we will convert into g/mile: In 15.000 miles, CO2 = (15 000 mnites)(359 gimite) = 5.38 x 10° g or 5.38 x 10° kg = 5.38 metric tons, The gasoline engine produces 266 g COx/km,Measurements 1-10. 114, 1-15. which we convert into 428 g/mile or 6.42 metric tons in 15 000 miles. : m Newton = foree = mass * acceleration = (3) Joule = energy = force x distance = vf Pascal = pressure = force /area = ss omgt (535 det” eg 1g (Holexk 7 (2) molarity = moles of solute / liter of solution (b) molality = moles of solute / kilogram of solvent (c) density = grams of substance / milliliter of substance (d) weight percent = 100 x (mass of substance/mass of solution or mixture) (e)_ 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 = 109 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 ina liter, the concentrations of CH3CO2H plus CH3CO3, add to 0.01 M. The concentration of CH3COH alone is less than 0.01 M, 32.0 g/ ((22,990 + 35.453) g/mol] = 0.548 mol NaCl 0.548 mol / 0.500 L = 1.10M [:7 ASO! 10 sta = 0.171 mol CH30H1-16. 1-17. 1-19. 1-21, Chapter | 017 mics te | = 548g 7 Ibar (a) 19 mPa = 19 * 10°3 Pa. 19x 103 Pe x = 19x 10-7 bar I cf (b) T(K) = 273.15 + °C = 273.15 - 70 = 203 K n PORT = 11x 108M = 119M Lgsolute 1 ppm 108 g solution Since | 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, | ppm = 103 g/L or | pg/mL. Since 103 g= 1 mg, | ppm= 1 mg/L. 0.2 ppb means 0.2 x 10-9 g of CooHla2 per g of rainwater ¢_ 8020 0.2 10° g C2oHs2 = 0.2% 1057000 g rainwater ~ ——_L rainwater 2106S /L 0.2 «1078 /E 7 gto 282.55 ¢ /mol (0 ros 8800 Jang gsolutioi) = 26.5 g HCIOg ion 37.6 g solution ~ 26.5 g HCIOg = 11.1. gH20 (a) ( on 2 ec (b) (070s gHCIOs ‘o 67x10? gsolution) = 1.18 x 103 g HCIOy 1,67 * 103 g solution L J (c) (1.18 « 103 f)/(100.46 gf /mol) = 11.7 mol iy = ol KL molality = Kg solvent 2002 Kl 200g KI 20.0. wt% KI = 7999 g solution ~ 800 ¢H20 To find the grams of KI in | kg of HzO, we set up a proportion:‘Measurements 1-22. 1-23. 1-24, 200gKI___x gk i 800 g 10 ~ 1000gH20 ~*~ 2508KI But 250 g KI = 1.51 mol KI, so the molality is 1.51 m. (a) 1SOX107S molioet _ emo! 9) 3.5 «104 vesiclesioott ~ 6° vessicle 23 molecules (6) (6.0 x 1078 wf (s 022 x 1073 Molesules | _ 3.6 x 105 molecules wot) 4 5 7 200 10°? m3 = 3.35 « 10-20 m3; (c) Volume 3.35 x 107%" : 23.35 1017L 108 IL 18, (a) eto Smet _ 939m 3.35 <10°7L x x10 80108 = 44x 104m, 242100 mol yy 103M; 180.2 £/ mol 100107 L Similarly, 120 mg/100L = 6.7 103M A Sotaeeciert ae (a) Mass of 1.000L = 1.0462 x 1000+ 1.000% = 1046 g ) na v x 8 snot L Grams of C2H6Q2 per liter = 6.067 (b) 1.000 L contains 376.6 g of CoHgO2 and 1 646 376.6 = 669 g of 20 = 0.669 ky 6.067 mol Cott .669 kg H: = mol C2H602 keno 907m Molality Shredded wheat: 1,000 g contains 0,099 ¢ protein + 0.799 g carbohydrate 0.099 f x 0 + 0.799 £ x40 CF 36 cal g Doughnut: 1,000 g contains 0.046 g protein + 0.514 g carbohydrate + 0.186 g fat tL Cal Cal 0.046 gf «4. af +0514 gf i * 0.186 <0 = 3.9Cal I Cal Ina similar manner, we find For hamburger and 0.48 “= for apple. There are 16 ounces in | pound, which Table I-4 says is equal to 453.592 37 g1-26. 1.27, 1.28, 1-29, Chapter 1 =a = 28.35 Sonos To convert Cal/g to Cal/ounce, multiply by 28.35: Shredded Wheat___Doughnut __Hamburger__ Apple Cal/g 3.6 39 2.8 0.48 Cal/ounce 102 i 79 14 ‘ Mass of water = x (225 pa)? (10.0 wl ae Jo hs 10° kg kg HzO Mass of F required = 1.6 «10 (1.5910 ke-Hs0) = 2.5% 105g F. (ifwe retain three digits for the next calculation, this last number is 2.54 108.) ‘The atomic mass of F is 18.998 and the formula mass of HoSiFs is 144.09. One mole of HpSiF'g contains 6 moles of F. mass of, _ Gx 18.998 254% 108 gE mass of HSiF ~ 144.09 TelhSifg = * = 32% 10° g HQSiF6 (@) PF = nkT (1.000 bari(5.24 * 106 L) = / 7 [0.08314 =) U mol K Son =2.11 % 10-7 mol => 2.11 10-7 M (b) Ar: €,934% means 0.009 34 L of Ar per L of air L- bar {1.600 bar)(0.009 34 L) = 2 (oss 4 (298.15 K) \ mol K/ =n =3,77* 10-4 mol = 3.77 104M Kr: 1.14 ppm = LI4pL KrperL ofair > 4.60 x 108M Xe: 87 ppb => 87 nL Xe per Lofair = 3.5 x 10M Bat g 61.83 x prof Weigh out 2 * 0.0500 mol = 0.100 mol = 6.18 g B(OH)3 and dissolve in 2.00 kg H20. 2.00 ¥ «0.050 0. = 6.18 gin a2 L volumetric flaskMeasurements 1-30. 131. 1-32. 1-33. 1-34. 1-35, Meon* Yeon = Mail Fait mol mol 0.80—- |(1.00 = 25— | Fait Vai = 3.2L ( met 4) (0 st) ‘él => Vail We need 1.00 ¥ * 0.10™> = 0.10 mol NaOH = 4.0 g Nat x“ v 0.10 mol NaOH = 4.0 g NaOH — =] = 80g solution 0.50 SOF gsolution , Mail M (@) Veon = Vait Men = = 1000 mL [13 5 Coke 55.6 mL (b) One liter of 98.0% H2SO4 contains (18.0 prof (98.079 g/ eof) = 1.77 x 103 g of HySO4. Since the solution contains 98.0 wt% HySOx, and the mass of HpSO4 per mL is 1.77 g, the mass of solution per milliliter (the density) is 1.77 gH2804 (mL 0.980 g H280; /g solution 2.00 L of 0.169 M NaOH = 0.338 mol NaOH = 13.5 g NaOH solution mL solution 13.5 géaOr 7 (16.7 mL solution) 0.534 v = 1.80 g solutionmL density = FM of Ba(NOs)2 = 261.34 4.35 g of solid with 23,2 w1% Ba(NO3)2 contains (0.232)(4.35 g) = 1.01 g Ba(NO3)2 1.01 g a ee = 3.86 * 103 mol mol H2$Oq = mol Ba2* = 3.86 x 10-3 mol ; (3.86 « 103 mol) volume of H2S0s = “355 moll = 1.29 mL. mol Ba2+ 25.0 mL of 0.023 6 M Th** contains (0.025 0 L)(0.023 6 M) = 5.90 x 104 mol Th** mol HF required for stoichiometric reaction = 4 x mol Th#+ = 2.36 x 10-3 mol 50% excess = 1.50(2.36 x 10°3 mol) = 3.54 « 10°3 mol HF10 1-36. 1.37. 1-38, 1-39. 1-40. 1-41. 1-42. 1-43. Chapter t Required mass of pure HF = (3.54 x 10-3 mol)(20.01 g/mol) = 0.0708 g (0.0708 gHf) i Mass of 0.491 wi% HF solution = —_CO™RS SAN) _ 108 (0.004 91 g HE /g solution) 44g Concentrations of reagents used in an analysis are determined either by weighing ‘out 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 px marked by a sudden change in a physical property brought about by the disappearance of a reactant or appearance of a product. , Which comes near the equivalence point, is 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 direetly with analyte. In a back titration, a known excess of reagent that reacts with analyte is used. The excess is then measured with a 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 = 1.60 mmol of Hg’ , which will require 3.20 3.20 mmol mmol of KI. This is contained in volume = 5799 mmovmL ~ 32-0 ml. 108.0 mL of 0.1650 M oxalic acid = 17.82 mmol, which requires 2 mol MnOg B mol HaCz0q) (17-82 mol H2C204) = 7.128 mmol of MnO, -Measurements 1-44, 1-45. 1-46, 7.128 mmol / (0.1650 mmol/mL) = 43.20 mL of KMnOy. Another way to see this is to note that the reagents are both 0.1650 M. Therefore, volume of MnOj = (volume of oxalic acid) . 5 See For second question, volume of oxalic acid = 3(volume of MnQj) = 270.0 mL, 1.69 mg of NH3 = 0.0992 mmol of NH. This will react with 3 (0.0992) = 0.149 mmol of OBr". The molarity of OBr' is 0.149 mmol/1.00 mL = 0.149 M. 3337 mol sulfamie acid = 57.694 gimol ~ 34369 mmol 3.4369 mmol molarity of NAOH = “3556 mp = 0.1003 M HCI added to powder = (10.00 mL)(1.396 M) = 13.96 mmol NaOH required = (39.96 mL)(0.1004 M) HCI consumed by carbonate = 13.96 ~ 4,012 = 9.94 mmol mol CaCO3 .012 mmol 3 mol HCI consumed = 4.974 mmol = 0.497g g CaCO3 0.4978 g CaCO3 = 5413 g limestone * 100 = 92.0 wi% wi% CaCOs24. 2-4, 2-5. 2-6. 2-8. 2-9. 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. Dichromate (Cr.03) is soluble in water and contains carcinogenic Cr(VI). Reducing Cr(VI) to Cr(II1) decreases the toxicity of the metal. Converting aqueous Cr(III) to solid Cr(OH)s decreases the solubility of the metal and therefore decreases its ability to be spread by water. Evaporation produces the minimum volume of waste. ‘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 1 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) ( 78.0 g/mL ) m=——F—0Tz gimLy — * [4858 "0.626 val) 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. 0.0012 g/mt. aes 366.8 8.0 g/mL m= (i TIT ml) 423918 71.636 g/mL Without correcting for buoyancy, we would think the mass of primary standard is less 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 a 100 = “Taap]* 100 = 0.06%.Tools of the Trade 13 2-11. (a) Onemol of He (= 4.003 g) occupies a volume of «pi ( ones Lipa ig ]O018) (293.15 K) BOK = 2437L I bat Density = 4.003 g/24.37 L = 0.164 g/L = 0.000 164 g/mL 0.000 164 pint. \ (0.823 oft | 8.0 9 (b) m= PTE 60 Be SHS 0.823 g 1 0.000 164 0.97 gin 2-12. (a) (0.42) (2330 Pa) = 979 Pa (b) Airdensity (0.003 485)(94 000) ~ (0.001 318)(979) 0.003 485) 24.0 = (0.001 318) 27) sty pf = 0.0011 pint (,_ 0.0011 plant 8.0 gin — SO re | = 1.00108 | 0.0011 gia 1.00 géett {6 370 000 my? (6 370.030 m)? (c) mass = 1.0000 g (100.0000 213. my = ims = 99.999 1g 2-14, TD means “to deliver” and TC means “to contain.” 2-15. Dissolve (0.2500 L)(0.1500 mol/L) = 0.03750 mol of K2SOq (= 6.535 g, FM 174.26 g/mol) 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. 2-46. The plastic flask is needed for trace analysis of analytes at ppb levels that might be lost by adsorption on the glass surface 2-17. (a) With a suction device, suck liquid up past the 5.00 mL mark. Discard one or two pipet volumes of liqu to rinse the pipet. Take up a third volume past the calibration mark and quickly replace the bulb with your index finger. (Alternatively, use an automatic suetion device that remains attached to the14 2-18. 2-19, 2-20. 2-21. 2-22, 2-23. Chapter 2 pipet.) Wipe excess liquid off the outside of the pipet with a clean tissue, Touch the tip of the pipet to the side of a beaker and drain liquid until the bottom of the meniscus reaches the center of the mark. Transfer the pipet to a receiving vessel and drain it by gravity while holding the tip against the wall After draining stops, hold the pipet to the wall for a few more seconds to complete draining. Do not blow out the last drop. The pipet should be nearly vertical at the end of delivery. (b) Transfer (a) Adjust the knob for 50.0 uL. Place a fresh tip tightly on the barrel. Depress the plunger to the first stop, corresponding to $0.0 uL. Hold the pipet vertically, dip it 3-5 mm into reagent solution, and slowly release the plunger to suck up liquid. Leave the tip in the liquid for a few more seconds. Withdraw the pipet vertically. Take up and discard three squirts of reagent to clean and wet the tip and fill it with vapor. To dispense liquid, touch the tip to the wall of the receiver and gently depress the plunger to the first stop. After a few seconds, depress the plunger further to squirt out the last liquid. (e ‘The procedure in (a) is called forward mode, For a foaming liquid, use reverse mode, Depress the plunger beyond the 50.0 jtL stop and take in more than 50.0 UL. To deliver 50.0 wL, depress the plunger to the first stop and not beyond. ‘The trap prevents liquid filtrate from being sucked into the vacuum system, The watchglass keeps dust out of the sample. Phosphorus pentoxide 20.2144 g— 10.2634 g = 9.9510.g. Column 3 of Table 2-7 tells us that the true volume is (9.951 0 g)(1.0029 mLig) = 9.979 9 mL. 0.999 1026 Expansion = ‘9979479 ~ 1-002 0608 = 0.2%. Densities were taken from Table 2-7. The 0.5000 M solution at 25° would be (0.500 0 M)/(1.002) = 0.4990 M. Using column 2 of Table 2-7, mass in vacuum = (50.037 mf )(0.998 207 | g/snt) = 49.947 g. 50.037 gat 1.0029 t/g, Using column 3, mass in air = = 49,892 g,Tools of the Trade 15 2-24, 2-25. 2.26. ‘When the solution is cooled to 20°C, the concentration will be higher than the : 7 density at 20°C : concentration at 24°C by a factor of Gensity at 24°C Therefore, the concentration needed at 24° will be tower than the concentration at 20°C. ‘setae ear] Desired itration at 24°C = (1,000 M) esired concentration at 24°C = (1.0 (See 0.999 1 M (using the quotient of densities from Table 2-7). The true mass of KNO3 needed is (0.5000 ufo 9991781) 101,103-5 = 50.506 g, (60506 g) (1 20012 zal) ee 2.109 eff 0.0012 gia.) = 50.484 g 1-30 g/mL m= \in specifications = e@™ 2m, Tf j,=2 yr and 1=2 yr, then specifications = e2(In2y2 (a) Fraction fraction wit (b) Fraction within specifications = 0.95 1n(0.95) = (In 2/2 => ¢= 2 1n(0.95)/In 2 = 0.148 yr= 54 days ~ 8 weeks To solve for ¢, take the natural logarithm of both sides: Alextracted from glass = (0.200 L)(5.2 x 10° M) = 1.04 x 10-6 mol mass of Al= (1.04 x 10-6 mol)(26.98 g/mol) = 28.1 1g This much Al was extracted from 0,50 g of glass, so 28.1 x 10-6 wt% Al extracted = 100 sag = 0.005 62 wi% 0.005 62 wt% Fraction of Al extracted = 9 -g9 yiaq_ = 0.007 0 (or 0.70% of the Al)16 2.27, (Graph of van Deemter Equation van Deemter Equation Plate height (mm) 0 2 4 6 8 Flow rate [Plate height (Constants |{mi/min) _|(mm) = zi 8.194) 6 6.092) 8 5.064 10) 4.4656) 20 3.412) 30 3.218 40) 3.239 50 3.346) 60, 3.496 70) 3.671 20) 3.861 20) 4.061 100] 4.268 Formula: C5 = SAS6+SASB/B5+SASIO"BS Flow rate (mL/min) 100 Chapter 23-2, 333. 3-4, 3-5. 3-6. 3-7. 3-10, 3-12. CHAPTER 3 EXPERIMENTAL ERROR @5 (b) 4 (3 (a) 1.237 (b) 1.238 (©) 0.135 (d) 2.1 (©) 2.00 (2) 0.217 (0) 0.216 (6) 9.217 (b) 1.18 ( significant figures) (c) 0.71 (2 significant figures) (a) 3.71 (b) 10.7 (c) 4.0 «10! (d) 2.85 ¥ 106 (©) 12.625 1(f) 6.0 104 (g) 242 (a) BaF2 = 137.327 + 2(18,998 403 2) = 175,324 because the atomic mass of Ba has only 3 decimal places. (b) Cotigg = 6(12.010 7) + 4(1.007 94) + 415.9994) = 140.0936 (The fourth-decimal place in the atomic mass of C has an uncertainty of + 8 and the fourth-decimal place of © has an uncertainty of + 3. These uncer- tainties are large enough to make the fourth-decimal place in molecular mass of Cot4O4 insignificant. Therefore, another good answer is 140.094.) (a) 123 (b) 75.5 (©) 5.520103 (a) 3.04 (e) 3.04% 10-10 (f) 19 (g) 4.600 (h) 4.9 10-7 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 eliminate it 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 isa systematic error, The pipet always delivers more than it is 718, 3-13. 3-14, 3-15. Chapter 3 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. (c) 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. (d)_ 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 (¢) Chastity (d) Chery! 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) 6.2(40.2) =4.1 (20.1) 2lse 9.22 +012 > e=0.2o4 Answer: 2.1 40.2 (or2.1 + 11%) {b) 9.43 (40.05) 9.43 (40.53%) 0.016 (40.001) => 0.016 (46.25%) %e? = 0.532 + 6.252 0.15088(=%e) => %e = 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), so we can rewrite the problem as 2.1 (0.294) + 9.43 (£0.05) = 2.1 (410.7%) + 9.43 (40.53%) %e = 10.72 + 0.532 = 10.7% Absolute uncertainty = 0.107 * 0.223 = 0.0239 Answer: 0.223 + 0.024 (119%) (d) The term in brackets is 6.2 (40.2) x 103 YO2P+012 > e=0.224 $4.1 40.1) «103 10.3 (40.234) x 103 = 10.3 x 103 (42.17%) 9.43 (40.53%) * 0.010 3 (22.17%) = 0.097 13 + 2.23% = 0.097 13 + 0.002 17 Answer: 0.097; + 0.0023 ( 2.2%)Experimental Error 19 3-16, (a) Uncertainty = [0.032 * 0.02? + 0.06? = 0.07 Answer: 10.18 (40.07) (40.7%) (b) 91.3 (1.0) * 40.3 (40.29/21.1 (40.2) = 91,3 (41.10%) x 40.3 (40.50% Y/21.1 (40.95%) % uncertainty = +f/1.10? + 0,50? + 0.952 = 1.54% Answer: 174 (23) (42%) (©) [4.97 20.05) ~ 1.86 (40.01)/21.1 (20.2) = [3.11 (40.0510))/21.1 (40.2) = [3.11 (£1.64%))/21.1 (40.95%) = 0.147 (41.90%) = 0.147 (40.003) (22%) (@) 2.0164 (0.0008) 1.233 (40.002) + 461 (20.01 7.8594 (0.000 8)2 + (0.0022 + @.01)2 = 0.0192, Answer: 7.86 (£0.01)(40.1%) (©) 20164 (£08) + 123.3 (40.2) + 46.1 (40.1) 2185.8 (0.8)? + (0.2) + (0.1)? = 0.8 Answer: 2185.8 (40.8) (£0.04%) () Fory X= 3.14 £0.05 => Vey = (0.05 /3.14) « 100 = 1.592% Y%ey = $ (1.592%) = 0.531% x4, %oey = a%ey Answer: 1.4643 & 0.007s (40.53%) (g) For y= log x, ey = 0.4342: x=3.1440,05 > ey = 0.43429 (2 (37g) = 0.006915 Answer: 0.4969 0.0069 (# 1.39%) 317. (@) y= 0.0175% (1.75 « 10-4) 3.1475 = 3.1 = 104 Answer: 1.77243 + 0.0003, (b) y = logx = ey = 04349 (SICH = 152« 104 Answer: 0.497 14 # 0.000 Is20 Chapter 3 (©) y = antilog x= 10° > ey =y x 2.3026 ey = (103-141 5)(2302.6)(0.001 1) = 3.51 Answer: 13852 # 0.0035 « 108 @ y= Inv > ey = goon = 35x 104 Answer: 1.1447 # 0.00035 (c) Numerator of log term: 03225 + 2.88% _ 0.3225 0.0511 = 0.0009 0.0511 + 1.76% = 6.311 £ 3.375% = 6.311 40.213 0.006 : (R906 100) = 2.88% For y= logx,ey = 0.43429 = 0.43429( 3) = 0.015 Answer: 0.809 + 0.015 3-18, (a) Standard uncertainty in atomic mass is equal to the uncertainty listed in the periodic table divided by «J3 because atomic mass has a rectangular distribution of values. Na = 22.98976928 + 0.000000 024/3 g/mol Cl = 35.453 £0,002A/3 g/mol 58.442 770 [(2 = 10°8)2y3 + [(2 « 10°3)2y3 = 1.2 103 58.443 + 0.0512 g/mol 5) molarity = 22 _ 12.634 C£0.002)x] /|58.443 (40.001)e/mol] emote eee 0.100000 (0.000 08) L _ 2.634 (£0.076%) / [58.443 (40.002 1%) Ma 0.100 00 (0.08%) relative error = >/(0.076%)? + (0.002 1%)? + (0.08% molarity = 0.4507 (40.000 5) M a) m ( dus da d 240,000 1) gh tio346 20,0002 (1-20 20.0001) gt) 319. m= 8.0 (40.5) g/ml. 0.007 2(£0,000 1) pint. 190.997 2995 gimL m=Experimental Error 2 3-20. 3-21. 3-22, 7 a 0.001 2 (48.33%) {1.0346 ow ¥0i(1- BOmeaH) moe 1 2:0012 (28.33%) ~0.9972995 (20%) _ 11.0346 (40.019 3%)//1 ~ 0.000 150 (10.4%)] an [1 0.001 203 @8.33%)] _ [1.0346 (40.019 3%)] [1 ~ 0.000 150 (20.000 015 6)) oe [1 = 0.001 203 (0.000 100)] _ 11.0346 (40.019 3%)] [0.999 850.0 (0.000 015 6) ueas [0.998797 (£0.000 100)] [1.034 6 (£0.019 3%)] [0.999 8500 (£0.001 56%)} BPE [0.998 797 (40.0100%)] m = 1.0357 (£0,021 8%) = 1.0357 (40.0002) g 277440.001g 0.2774, 0.0018 159.688 gimol ~ 159.688 * 159.688 1,737] # 0.0113 mmol Fe203 mass of Fe = 2{1.7371 (40.0113) * 10-3 mol)[55.845 g/mol] = 0.1940: mass of Fe per tablet = (0.19492 + 0.00126 g)/12 = 16.163 + 0.195 mg = 16.2£0.1 mg mol Fe03 = 00126 g mol H* = 2.x mol NaxCO3 _ 0.9674 (40,0009) 2 __0.9674 (0.093%) ¢ mol Na2CO3 = {93 988 4 («0.000 7) g/mol ~ 105.988 20.000 66%) gimol = 0.009 1274 (40,093%) mol mol H* = 2(0,009 127.4 (20.093%6)) = 0.018.255 (40.093%) mol (Relative error is nat affected by the multiplication by 2 because mol H* and uncertainty in mol H* are both multiplied by 2.) __ 0.018255 (40.093%) mol _ 0.018 255 (0.093%) mol molarity of HCl = “9 99735 (£0,00004) L_ ~ 0.02735 (40.146%) L = 0.66746 (20.1739) = 0.667 46 (20.001 155) = 0.667 £ 0.001 M To find the uncertainty in co3, we use the function y = x in Table 3-1, where x = cy and a = 3. The uncertainty in ¢43 is Yaty = a%eey = 3% a x 2 % 100 = 1.823 x 105% So cg} = (5.431 020 36 * 10-8 em)} = 1.601 932 796 0 x 10-7? cm? with a2 3-23, Chapter 3 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.) The value of Avogadro's number is computed as follows: Si 28,085 384 2 g/mol © (pea 8 ~ (2.329 031 9 glem3 « 1.601 932 7969 « 1022 emsy/& = 6.022 136 936 1 x 1023 molt Na The relative uncertainty in Avogadro's number is found from the relative uncertainties in msi, 2, and co}. (There is no uncertainty in the number 8 atoms/unit cell.) 00 (0.000 003 5/28.085 384 2) = 1.246 x 105% percent uncertainty in = 100 (0.000 001 8/2.329 031 9) = 7.729 x 105% percent uncertainty in co? = 1.823 * 10°5% (calculated before) percent uncertainty in msi percent uncertainty in Va = «/%ems2 * %er + (%ee,3) = [1.246% 105) + (7.729% 10-5)? + (1.823 * 105)2 = 8.038 x 10°5% The absolute uncertainty in Na is (8.038 * 10°5%)(6.022 136 936 1 1023)/100 = 0,000 004 841 « 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: = 6.022 136 9 (£0.000 004 8) * 1075 or 6.022 136 9 (48) x 1023 C: 12.0107 + 0.000 84/3; HI: 1.00794 «0.000073 O: 15.9994 + 0,000 34/3; N: 14,096 7 + 0.000 24/3 +9C: 9(12.0107 + 0.0004.) 108.096 3 = 0.004 2 +9H: 9(1.007 94 + 0.000 040) 9.071 46 + 0,000 36 +60: 6(15,9994 + 0,000 17) 95.996 4 0.001 0 +3N:_ 3(14.0067 + 0.000 13) 42,020 1 0.000 35 CoHoOgN3 255.184 264? Uncertainty = 0.004 22 + 0.000 36? + 0.001 02 + 0,000 352 = 0.004 Answer: 255.184 + 0.004Experimental Error - 3-24, Relative uncertainties: Large volume: 0.000 5 L/5.013 82 L = 0.010% Small volume: 0,000 9 mL/3.793 0 mL = 0.024% Pressure: 0.03 mmv/400 mm = 0.008% Temperature: 0.03 K/300 K = 0.01% The largest uncertainty is in the volume of the small vessel = 0.024%, Uncertainty in CO. ~ 0.024% of 400 ppm = 0.000 24 x 400 ppm = 0.1 ppm.41. 43. 44, 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 pertains to precision, not accuracy. -ltoz = +1. The area fromz = Otoz = +1 is (a) #0 corresponds toz 0.341 3. The area fro Total area (= fraction of population) from 2toz=+2 = area=2% 0.4773 = 0.9546 —L is also 0.341 3, toz (b) (©) z=0to z= 1 => area=0.3413 (d) 2=0toz=0.5 = area=0.1915 1 to2 =O is 0.34! 3. Area from z=~0.5 toz=0 is 0.1915. 1 toz=~0.5 is 0.3413 -0.1915 =0.1498, (e) Area from z Area from (2) Mean = (1.526 60 + 1.52974 + 1.52592 + 1.52731 + 1.52894 + 1.52804 + 1.52685 + 1.52793) = 1.52767 (b) Standard deviation = 0.001 26 (c) Variance = (0.001 26)? = 1.59 = 106 (d)_ Significant figures: ¥ +s = 1.527; 40.0015 or 1.528 £ 0.001. (1005.3 — 845,2)/94.2 = 1.700. 4. The area above (a) 1005.3 hours corresponds t In Table 4-1, the area from the mean to 2 = 1.700 is 0.45: 1.700 is therefore 0.5 ~ 0.455 4 = 0.044 6, 798.1 - 845.2)/94.2 = -0.500. 0.500 is the same as the area from the mean to (b) 798.1 corresponds to z The area from the mean to 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 z = 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 (c) The following spreadsheet shows that the area from —2 to 800 h is 0.315 7Statistics 25 and the area from —20 to 900 h is 0.719 6. Therefore, the area from 800 to 900 h is 0.719 6 ~ 0.315 7 = 0.404 0. A B c 4 |Mean = ‘Sid dev = 2 8482 942 3 4 [Area from ~» to 800 = 0.3187] S lareafrom-.to900= 0.7198) § |Area from 800 to 900 0.4040) 7 i 3 |C4 = NORMDIST(600 SAS2,$882, TRUE) 9 C5 = NORMDIST(900,SAS2,$882, TRUE) 40 |C6 = C5-C4 4-5, (a) Half the people with tumors have K < 0.92 and would not be identified by the test. The false negative rate is 50%, (b) The false positive rate is the fraction of healthy people with K > 0.92. To use Table 4-1, we need to convert x = 0.92 to az value defined as In Table 4-1, area from mean = 2.4 is 0.491 8. Area from mean to 2.5 is 0.493 8. We estimate that area from mean to z = 2.43 is alittle greater than 0.492. Area above z= 2.43 is therefore 0.5 ~ 0.492 = 0,008. That is, 0.8% of healthy people will have a false positive indication of cancer In the following spreadsheet, cell ES computes the area below K = 0.92 with the formula NORMDIST(0.92, SBS4,$BS5,True), where B4 contains K and found in cell .007 6, BS contains the standard deviation, The area below 0.92 i to be 0.992 4, The area above K = 0.92 is therefore | ~ 0.002 4 A B c D E F c BH 7 | Gaussian distribution for phase partitioning of plasma proteins 2 “3 |Healthy patients i For healthy people, Area below cutoff @]MeanK= 0.75) ‘ea below 0.92 for people with tumors 5 s= 0.07 0.992421 Cutoff (kK) Area |Malignant tumor area above 0.92 = 0.8. 0.137656] 7|MeanK= 092 0.007579 0.81) 0.188655} 8 = ott 0.82) 0.181651 9 ‘area below 0.845 = 0.83) 0.206627| 10 0.912632 0.84) 0.233529] i ‘area above 0.845 = 0.85. 0.26227| 12 0.087368. 0.845, 0.247677| 13 145 = NORMDIST(0.92,$8$4,8885,TRUE) _H6 = NORMDIST(G8.S887.9588,TRUE) 2526 Chapter 4 (c)_ In column G, we vary the value of K and compute the area above K under the curve for people with malignant tumors in column H. We search for the value of K that gives an area of 0.25, which means that 25% of people with tumors will not be identified. The value 0.84 gives an area of 0.233 5 and the value 0.85 gives an area of 0.262 3. By trial and error, we find that K = 0.845 gives an area near 0.25, In cell E10, we insert K = 0.845 into the NORMDIST function for healthy people and find that the area below K'= 0.845 is 0.912 6. The area above K = 0.845 is 1 0.912 6 = 0.087 4, That is, 8.7% of healthy people will produce a false positive result, indicating the presence of a tumor, 4-6. x 5 c D E E S a 7 [Gaussian curve Tor ight bubs z Z]mean= x (hours) y (oubs) Formula for coll C2 = 4 845.2/ 500) 0.49 (SASBTSASTONSASB'SAST2))" [ste dev = 5251.25. EXP(((B4-$A84)"2)(2"SAS02)) oie 6 942, 550, 2.98 7 ical bubs = 600, 13.64 @ 4768 «625: 26.28 ‘[oulbs perbar: 650), 47.19 10 20. 675.7395 TH Jsaet2 i) = 700,423.41 2} 2508628 725. «178.92 13 760 242.35 14 775, 30584 |g 300 15 800 3s0a4 | 3 16 825, 39488 | 250 17 2452 40385 «| & 18 50, 4033 | 2 2 i 375, 384.14” | 3 450 20. 00, 34099 2 925 28208 100 2 960! 21750 2 975,156.29 80 24 4000. 10467 25 4025.65.93 . 28 4030" 38.00 400600 8010001200 ar 1075, 20.60 Litetime (hy 7 28 1100.10.41 2 1125; 490 [30] 1150, 218 31 1175, 88. EEEEEree| 32 200° 034Statistics 27 4-7. Use the same spreadsheet as in the previous problem, but vary the standard deviation, Here are the results: 8 Number of light bulbs 600 800 1000 1200 Hours 4-8. A confidence interval is a region around the measured mean in which the true mean is likely to lic: If we were to repeat a set of » measurements many times and compute the mean and standard deviation for each set, the 95% confidence interval would include the true population mean (whose value we do not know) in 95% of the sets of 7 measurements. 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. See 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. Use the F test to decide if the two standard deviations are significantly different. Case 3: Comparing individual differences. (Use Equations 4-10 and 4-11.) ¥ = O.14s, 5 = 0.034 (2.015)(0.034) 90% confidence interval = 0.145 + v6 = O.14g 0.023 99% conlidence interval = 0,14g+ 2P2XO09 _ 9 44 f confidence interval Ss Ve = 0.145 05628 4-13, 414, 4-15, Chapter (3.707)(0.00007) _ = Ps Vi + 0.000 10 99% confidence interval = (1.527 83 to 1.52803) (a) dL = deciliter = 0.1 L= 100 mL. (D) Featcutated = (0.053/0.042)? = 1.59 < Fiabte = 6.26 (for 5 degrees of freedom in the numerator and 4 degrees of freedom in the denominator). Since Feateutated < Fable We can use the following equations: (0.53%(5) + 0.42(4) DOD _ og, Spooted ~ 6+5 2.262 (listed for 95% confidence and 0.484 9 degrees of freedom). The results agree and the traince should be released. A B c o E F [Comparison of two methods 2 3 | Sample | Method 1 Method 2), a] A O88 083 | 008 = Baca 5| 8 1154.04 0.11 6] Cc 122439 | -0.17 7] 0 093 ost 0.02 e| & 1171.08 70.09 a] F 1.51 431 0.20 10 mean =" 0.050 14 stdev =, 0.124 12 eves = | 0.987 | = D10/017°SQRT(6) 3 toon =) 2.571 INV(0.05,5) ateuiuee = 0.987 < 2,571 (Student's 1 for 95% confidence and 5 deg of freedom) The difference is not significant. In the following spreadsheet, we find feajculated (Which is labeled t Stat in cell F10) is less than fable (t Critical two-tail in cell F14). Therefore, the difference between the methods is of significant, The probability P(T<=1) two-tail in cell F13 is 0.37. There is a 37% chance of finding the observed difference between equivalent methods by random variations in results, The probability would have to be <0.05 for us to conclude that the methods differ.Statistics 29 A I BS I c [oT E I FT Cc T [Parad eat 1 ‘Test Paved Two Sempla fo Means z | S|. Sample | Method | Method? __§ [rn re] a} A 028 | 088 Mean 714983955 109059009 3} 8 419 ‘08 ‘Variance 0105110867) 0.04616607 o] oc iz 139 Observations 6 4 75 093 O31 “Pearson Corian easHiai8| a} e sat 408 Hypotnesized Mean biference a a] oF tsi | 431 of 5 10; “Stat A 7 [Catan SRST CaN FIO (Te oneal ‘O-78at0079 [iafess than cial noel Fa {Crial onet 2.01508918) 73] Therfore, the difference between the |P(T<=t) two-tail ~0.36899857 “ra}menads snot signin.) {Crtical wo [esrosrrs9] 4-16. Featculated = 82%/s12 = (0.039)2/(0.025) = 2.43 Faable = 9.28 for 3 degrees of freedom in the numerator and denominator Since Featculated < Ftable, the difference in standard deviation is not significant and we use Equations 4-8 and 4-9. 51? (ty ~ 1) #52? (mg~ 1) (0.0252 (4 — 1) + 0.0397 (4-1) _ spot DEE oD 444-2 eae ey = 9] mir: 1,382~ 1.346) [4-4 3 mm 0.032 § aaa hable (4 + 4-2 =6 degrees of freedom) = 2.447 Since ‘calculated < fable, the difference is not significant. 1.55 fealeulated 4-17. For Method 1, we compute ¥1 = 0.082 6052, 5) = 0.000 0134. For Method 2, %2 = 0.082 005, 52 = 0.000 129. The two standard deviations differ by approximately a factor of 10, We should use the test to compare the twa standard deviations: Featculated = $2°/s1? = (0.000 12s)2/(0.000 0134)? = 92.7 Frable = 6.26. Since Featculated > Fable, We use Equations 4-8a and 4-9a, The following spreadsheet shows that fcalculated = 11.3 and fable = 2.57. Ialculated > fable, 80 the difference is significant at the 95% confidence level.30 Chapter 4 Paired ttest [Test Two-Sample Assuming Unequal Variances Method 1 Method 2 Variable T Variable 2. 0.08183,_[Mean 0.082605 0.082005} (0.08186) [Variance 4.8E-10) 1.67£-08 0.082589) 0.08205) Observations 5 0.082817) 0.08206) Hypothesized Mean Difference O 0.082598) 0.08215 5 | 0.08208 |14,81371 —Fealculsted = 11.3 I 4) one-tail (4.72605, | { Cfticl one tail | 2.016049 P(T<=t) two-tail 9.43E-05 Critical two-tail 2.570578 <— fable = 2.57 4-18. 90% confidence interval = ¥= £ 1.19% < 1.2%, The answer is yes. 4-19, For indicators 1 and 2: Feateulated = (0.002 25/0,000 98)? = 5.27 > Fiabte* 2.2 (for 27 degrees of freedom in the numerator and 17 degrees of freedom in the denominator). Since Featculated > Fiable, We use the following equations: Degrees of freedom _ (0.002 252/28 + 0.000 982/18)? __ 4 ~ (0.002 252/28)? (0.000 9827182 ~ 7°.8* 40 2-1 18-1 - feel _ __(0.095 65 0.08686 __ |. ‘eateuted =" F2imy + ing V0.002 252/28 + 0.000 982718 This is much greater than ¢ for 40 degrees of freedom, wl ‘The difference is 2.02. ificant. For indicators 2 and 3: Featculated = (0.001 13/0.000 98)? = 1.33 < Fiabe = 2.2 (for 28 degrees of freedom in the numerator and 17 degrees of freedom in the denominator). Since Featcutated < Fiable, We use the following equations: S12 (m ~ +83? 2-1) a? = 0.001 0758 myn = 1.39 < 2.02 = difference is not significant, ny enyStatistics 4-20. 4-21. 4-22, 31 Spooted = 32:32 37537 = 2:88. The table gives / for 60 degrees of freedom, which is close to 62. The difference is significant at the 95 and 99% levels. = 97.09, 8 = 1.66 ts (2.776)(1.66) + 5 #2 7 97002 97.09 + 2.06 95% confidence interval = ¥ Range = 94.94 t0 99.06 ‘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 ¥ = 96.53, 8 = 1.89 2.571180) 95% confidence interval = 96.5g 96.53 + 1.89 Range = 94.69 to 98.4 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: Feaiutated = (0.008/0.005)2 56 < Fable = 4.53 (for 4 degrees of freedom in the numerator and 6 degrees of freedom in the denominator). Since Featculated < Fable. We use the following equations: (0.0052(6) + 0.0082(4) Spooled = >\ [20st 08 = 0.00637 5 0.069 ~ 0.063 Tealculated = ‘The difference Drinking water: Feealculated = (0.008/0.007)2 = 1.31 < Fiabe = 6.39 (for 4 degrees of freedom in the numerator and 4 degrees of freedom in the denominator). Since Fealcutated < Fable, We use the following equations: (0.00724) + 0.0082(4) Spooled = 345-2 = 0.00752 0.087 ~ 0.078 0.00752 go < 2.306. The difference is noi significant.32 Chapter + {b) Gas chromatography: '0.0052(6) + 0.0072(4) 2 Spooled = 745 = 0.00535 0.078 ~ 0,069, [7-5 1) 005g Fry = 261 > 2.228. The difference is significant. Spectrophotometry: 0.0082(4) + 0.0082(4) Spooted = = 0.00899 0.087 ~ 0.063 5. = 9.00859 \ sr 5 7 474> 2.306. The difference 201.8: Gealculated significant. 4-23. 9.34 216 - 201.8) /9.3 Gable = 1.672 for five measurements Because Geatculated < Grable, We should retain 216, 4-24, Slope = ~1.298 72 x 104 (40.001 3190 = 104) = =1.299 (£0.001) * 104 or 1,298; (40.0013) x 104 Intercept = 256.695 (4323.57) = 3 (43) x 102 4-25. Xi vi xvi xt dj ad 0 0 007143 0.00510 4 4 0.21429 0.04592 9 9 0.14286 0.02041 sams: 3 B BO 0.07143 nets = = 3 = 064286 mo = a" Zor?) Epi Ee) xj _ 13 «6-13«5 _ 13 = yee? So 352 = 0.928 57 nx?) (Eu? 353 faeStatistics 33 Le) ee aera 1 = 0.26726 4 Sy = Sy \frwaran 0.12371 2 5 4 2 13 4 Sb = sy oxoro/8 i = 0.25754 ° . 1 ; o 1 2 8 slope = 0.64 £0.12 intercept = 0.93 + 0.26 te 4-26. 6 y = O.6164x + 1.3462 5 4 a3 1 ° o + 29 4 5 6 4-27. A I 8 Cc D E F GS H Tk y 2 30. 0.074 1 Ts] 100° att 4 20.0 -2,584, o 3] 300-3750 6 40.0 5.407 | a 7 2 ey LINEST output - ro] [0.13789 0.195303] 3 10 snf 0.006635. 0.162763}, 7 4 R'] o.g93102_0.187625]s, : 72 73 Highlight cells BS:C14 6 (74) type ne ee a) [5] "=LINEST(62:86,42:46,TRUE,TRUE)" x [6] Press CTRL*SHIFT+ENTER (on PC) 17 [Press CONMAND+RETURN (on Wc)34 4-28, 4-29. 4-30. 431. Chapter 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. Hopefillly, the negative value is within experimental error of 0. Ifso, 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 pg Pa(Qe3r445\4=3.5 (L43 444 643.5 Leyj-xP? = (1- 3.52 + (3 ~ 3.5)? + (4 —3.5)2 + (6 - 3.5)? = 13.0 -2 Ady Sx In \f ea Rin ? 0.19612) ft _2.58=357 _ (0.61538) \J1 "4 * (615 38)2 (13.0) ~ 08 4 Answer: 2.09 0.38 (b) For k=4 replicate measurements, _ 0.19612 | fl 1 @58=3.52 [0.61538 \/4"4 * (615387 (13.0) ~ 076 Answer: 2.09 + 0.26Statistics 35 4-32, Mean absorbance = (0.265 + 0,269 + 0.272 + 0.258)/4 = 0.2660 Mean blank: (0.099 + 0.091 + 0.101 + 0.0974 = 0.097 2669 ~ 0.097 = 0.16% Cells B30 and B3 lof the spreadsheet show that there are 10.1 # 0.2 1g protein. = Corrected absorbance = x at o = F S a 7 T [toast Squares Spreadsheet i 2 3 Seay | Ca ; 5 ae 3 00.0007 03 7 50.0867 3 500877] 9 50.0887] 10 +0" 0.1827] 028 7H 10, 0.1727] 2 | to over] 13 15,_0.2487| g 02 14 180.2877] I g is an asas7} 8 16 20, 0.3287] 3 a7 20' 0.3307] 2 ons 8 18 LINEST ouiput 20 im 0.07630, 0.00870] ra 21 3_| 0.00022 0.002855 2 R/ 0.99785) 0.00586|s, 3 2aIn = 4+4'p24 = COUNT(@4:817) 25 |Mean y= 0.46184 825 = AVERAGE(C4:CI7) 26 [E(x mean x= 723.214 826 = DEVSQ(B4:517) a7 T ° ZB [Measured y= _ [O7E5]input | o 5 0 8 INumber of hoe Protein (ug) measurements 29 fof yk) = sfirout ZODerivedx 70,082,821 = (628-C20)1620 34). ‘0.2045 831 = (C22"B 20 SCAT (C1828) +1784) +((626-025)'2}/(620°2"826))36 Chapter 4 4-33. (a) A re eee eee ee Ee] F T 6 7 4 T 7 T]teast Squares Spreadsheet ___ | z i Ea x ewes 1600 | y= 669.19x- 22.085 a cs 3] ‘91062) a78 1200 é 0422, 6.5) 98.6 7 0.245 1847] 192.8 alee 8 0486 378.4 987.5 F 1000 3 cori e034 or28. = 70) igo 1652.6} 1671.9 = 00 ct 2 1 ____LINEST output ® 600 13] ‘| _869.15 -22.0852)5 400 14 Sm] 10.6422 8.94745, 15, R‘| 0.9903, 18.0527]5, 200 ig] i ° i7]n= (7 Bi? = CouNT(sAB10) 18 |vean y= 480.6 B18 = AVERAGE (C4:C10) PEPE eee etre ete 419 2(s,- mean x)=" 2.67757 819 = DEVSQ(e4:B10) eran eee 2) 7 21 Measured y= [TBO input Number of replicate measurements zafoty (K) = fino 23|Deivedx _O.TSEEH 823 = (82i-Ci3)813 24|3,.= 0.0137 B24 = (C15/613)'SQRT((1/822)+(1/817}+((B21-816)'2B13°2°819)) (b) Corrected signal = 154.0 ~9.0 = 145.0 mV (©) Cells B23 and B24 give [CH4] = 0.192 (40.014) vol% 4-34. 0.350 = -1.17 x 10-4 x2 + 0.018 58. ~ 0.0007 1.17 x 10-4 x2 0.018 58.x + 0.3507 = 0 yy = 10,018.58 + V0.018 582 —4 (1.17 « 10%) (0.3507) 2 (1.17 « 104) Correct answer is 21.9 pg. 137 of 21.9 ugStatistics 37 4.35. (a) The logarithmic graph spreads out the data and is linear over the entire range, 000 5000 Linear plot 4000 3000 Current (nA) log (nA) 2000 y= 17.083x + 92.183 0 © 100-200 300400 P-Nitrophenol (yg/mL) Jog (ug/ml) (b) log (current, nA) = 0.969 2 log (concentration, jg/mL) + 1.339 (0) log (99.9) = 0.9692 log [X] + 1.339 => log (X]=0.6816 = [X]=4.80 pg/mL 4-36. For 8 degrees of freedom, fop% = 1.860 and f99% = 3.355. 90% confidence interval: 15.22 (£1.860 * 0.45) = 15.22 # 0.86 Hg 99% confidence interval: 15.29 (3.355 * 0.4) = 15.2 + Ls ngCHAPTERS 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 collected properly and data has demonstrated reliability. zht: Record keeping should document that samples were The three parts of quality assurance are defining use objectives, setting specifications, and assessing results, Use objectives: Question: Why do { want the data and results and how will [use them? Actions: Write use objectives. Specifications uestion: 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 | 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 sampie. Accuracy is demonstrated by analyzing certified reference materials, by comparing results from different analytical methods, by fortification (spike) recovery, by standard additions, by calibration checks, blanks, and quality control samples (blind samples). Rene data are directly measured quantities, such as peak area in a chromatogram or volume from a buret. Treated dater 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, 38Quality Assurance and Calibration Methods 39 5-5. 5-6. 5-7. 5-9, 5-10, A calibration check is an analysis ofa 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 ion formulated by someone other than the analyst to alysis of a solu contain a known concentration of analyte. It is a test to see if the analyst gets the right answer when he of she docs net know the right answer. A blank is a sample intended to contain ne analyte. Positive response to the blank arises from analyte impurities in reagents and equipment and from interference by other species. A method blank is taken through all steps in a chemi al 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 useable 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 analyte exceeds a certain limit when, in fact, it is below the limit. A false negative is a conclusion that analyte is below a certain limit when, in fact, it 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 the detection limit. Therefore, 50% of samples containing analyte at the detection limit will be reported as not containing analyte ata 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 (I) 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 the center line, (4) six consecutive measurements, all steadily increasing or all40 5-13. 5-14, Chapter 5 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 (¢) is correct. The purpose of the analysis is to see if concentrations are in compliance with (in other words, 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 li nit should be higher than the instrument detection limit Robustness is the ability of an analytical method to be unaffected by small, deliberate changes in operating parameters. Intermediate precision 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 intermediate precision, 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. 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 1g equipment and reagents belonging to each lab times a Criteria: © Observations outside action lines — no * 2 out of 3 consecutive measurements between warning and action lines — noQuality Assurance and Calibration Methods 41 7 consecutive measurements all above or all below the center line — YES: observations 2-10 (starting from the left side) are all below the center line * 6 consecutive measurements steadily increasing or steadily decreasing —~ no 14 consecutive points alternating up and down — no Obvious nonrandom pattem — no 5-15, LINEST gives m, b, Sm, 8s, R°, and 5; in cells B19:C21. TRENDLINE produces the same value of m, 6, and R°, which are printed inside the graph. The 95% confidence interval for y is computed in cell C24. R 3 c D = E Sc 7 T |Grephing data with random Gaussian nowe i 2 |Generating equation: y = 26.4x+1.37 t 3_|Gaussian noise = 80) 4 2500 Hoy y=24207«-+ 80.727 6 0 14 R? = 0.9932 | 40 |) 350 2000 @| 20 | 666 | 30987 40 40 1067 ae 44 50 1364 7 72] 60 1573 13 70 1732 ae 44) 802480 45] 99-2380 500 16] 1002508 17 | Error bars are # t's in cell O24 18 LINEST output 0 79 imp 24e0727_ 872727] 0 2% 4 «60100 20 9.683532 40.49827]5, x 2 asea214 _71.6894)5, 23 ‘Students 2.262159] L 24 vs,[ 162.1726] 5-16, {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. 5.63 Precision = 100 x 23.8%. 23.66 2 Accuracy = 6.6% For the fortification level of 88.2 ng/mL and the standard deviation is 11.49 ng/mL. i149 : Precision = 100% gyqg = 13.9% mL, the mean of the 5 values is 82.4ga2 Chapter 5 82.48 ~ 88.2 Accuracy = 100 x 38.2—~CO 6.5% For the fortification level of 314 ng/mL, the mean of the 5 values is 302.8 ng/mL and the standard deviation is 23.5) ng/mL. : 23 Sie Precision = 100 395g = 7.8% 302.8 ~314 Accuracy = 100% 3g = 3.6% (b) Standard deviation of 10 samples: s = 28.2; mean blank: yolank = 45.0 Signal detection limit = yptank + 3s = 45.0 + (3)(28.2) = 129.6 3s _ __G)(28.2) ; eee Hs ) ag 108 Concentration detection limit = 35 = Tae jet 748 * 108M los __ 28. Lower limit of quantitation = 7 = Ss =1.6* 107M (a) Lwi% = C= 0.01: CV(%) = 2-05 108001) = 22 = 4% If C= 10°12, CV(%) = 27 = 128%, (b) If class CV is 50% of the value given by the Horwitz curve, it would be 0.5 2(1-0.510g0.1) = 1.4%, 5-18. Mean = 0.383 ng/L and standard deviation = 0.0214 ug/L 0.383 pg/L Y recovery = “FG yagi * 100 = 96% ‘The measurements are already expressed in concentration units. The concentration detection limit is 3 times the standard deviation = 3(0.0214 ug/L) = 0.064 pe/L. 5-19, The low concentration of Ni-EDTA has a standard deviation of 28.2 counts for 10 measurements. The detection limit is estimated to be Yolank +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 _ _Ysample~Yolank___ 1797-45 _ my = —2sample= lank _ 179° S75) x 1p Sounts 1,00 #M The minimum detectable concentration isQuality Assurance and Calibration Methods 43 35 _ _G)282)counts_ _ yo, sas my = 7.752% 109 counts ~ 48% 108M 5-20. For a concentration of 0.2 ug/L, the relative standard deviation of 14.4% corresponds to (0.144)(0.2 g/L) = 0.028 8 pg/L. The detection limit is 3(0.028. 8 pg/L) = 0.086 pg/L. Here are the results for the other concentrations Concentration Relative standard Concentration standard Detection (ug/L) deviation (%) deviation (ug/L) limit (ug/L) 02 144 0.028 8 0.086 0s 68 0.0340 0.102 1.0 3.2 0.0320 0.096 20 19 0.038 0 oud mean detection limit: 0.10 5-21. [fan 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. 5-22. Comparison of Lab C with Lab A: First, use the F test to see if the standard deviations are significantly different: Feateutated = 82/52 = 0.782/0,142 = 31.9 > Fiable = 3.88 (with 2 degrees of freedom for sc and 12 degrees of freedom for sa) Standard deviations are not equivalent, so use the following 1 test aa (s12/ny + 522/np)? _, (0.142/13 + 0.782/3)2 . Degrees of freedom = Gon? (eating = W.AGIRE O.TRIDE ~ 203 ~ 2 ny-1 B=) 7 3-1 pee ¥2|____|.59- 2.68 = 24 serene [stim + Bing VONRIS + 0.7873 ~~ For 2 degrees of freedom, fable = 4.303 for 95% confidence. Since fealoulated < m ‘table, We conclude that the difference between Lab C and Lab A is not significant.44 5-23. 5-24, Chapter 5 Comparison of Lab C with Lab Bz = 0.78210,562 1.94 intercept = 8.21 “10 ° 10 20 30 40 ig alliinig of garlic (a) In cells B20 and B27 of the spreadsheet, the negative x-intercept of the standard addition graph is 8.21 £ 0.62 mg alliin/g garlic. (b) Two moles of alliin (FM 177.2) produce one mole of allicin (FM 162.3) in the assay. Therefore, the quantity of allicin in garlic is ¥(162.3/177.2)(8.21 0,62 mg/g) = 3.76 + 0.2 slic or 3.8 £03 m garlic. Hlicin’g mg allicin/ 5-29. 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 ofa 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 dard conditions vary from run to run, Variations affect the analyte and sta 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 A 530, (0) (10222 oa : (aa 0.1684 > Barmy ~ “I Dat) at (1.00 (b) [8] = (847M) (ToomL) 0.847 mM Ax _ (ds © BT > MUS 5428 4431 Ty 79 1684 (Rea mA) => [X]=6.16mM5-32, Chapter 5 (d) The original c concentrati centration of [X] was twice as great as the diluted so [X] = 12.3 mM. For the standard mixture: Ax (8) 10.1 WA ( 15.3 uA F\Is)) = [0.800 my = * \f.s00'mmy, = F= 0.4126 Chloroform added to unknown = (10.2 * 10-6 L)(1 484 g/L) = 0.015 14g = 0.126g mmol in 0.100 L = 1.26; mM ix) For the unknown mixture: dx _ (ds) 8.7 uA (294A ) Bx > F\gsy) = TXT = 84126 26pm] = [X= 0.909 mt 100 mL) [DDT] in unknown = (0.909 mM) ate = 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, 1.0759, is the response factor. Over the concentration ratio analyle/standard = 0.10 to 1.00, the standard deviation of the response Factor in the table is 0.06¢g = 6.2%. Sample Area ratio Fe CyoHy/CioDs___area ratio/eone. ra 1 0.101 1.0127 2 0.573 L141 3 1.072 1.0724 mean = 1.0757 standard deviation 0.0665 relative stQuality Assurance and Calibration Methods sl 5-33. y = 1.0757x + 0.0085 08 06 Area ratio os 02 09 09 02 04 08 08 10 Concentration atio To use the internal standard, a known quantity of internal standard is added to a sample of sewage. Analyte signal is measured relative to the signal from internal standard. Since the internal standard is so similar to analyte (differing only by the substitution of D for H), matrix effects are likely to be essentially identical for both compounds. If matrix enhances the response to analyte, it enhances the response to internal standard to the same extent. By measuring unknown relative to the known injection of standard, an accurate measurement of unknown can be made. The Key is to use a standard that is almost identical to the analyte in physical properties,52 Chapter 5 5-34. Molarities are given in row 12 of the followin; spreadsheet and uncertainties are given in row 13: A B c D L E [Experimental Design 2 3 |Volumes of unknown acids (mL) mmol 4 A 8 Cc NaOH s[ 2 2 2] 3.015 6} 0 2 2 | 1385 Ht 2 oO 2 2.180 8 2 2 oO 2.548 g 2 2 2 3.140 410 11 cl 8) Al 12 Molarity| 0.25635 0.44035. 0.83785] 13 std. dev.| 0.026729 0.026729" 0.028729] 14 0.995942 0.063896. #N/A 15 R xy 16 | Highlight cells C12:E14 17 |Type “=LINEST(D5:D9,A5:C9,FALSE, TRUE)" 78 |Pross CTRL+SHIET*ENTER (on PC) 19 |Press COMMAND+RETURN (on Mac)6-1. 6-3. 6-4. 6-5. 6-6. 6-7. 6-8. 6-9. 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 | 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. (a) K=W{Ag*P [POX] (0) K = Peo$/ Po!3? 3.6 « 104 Torr bar) : Ee Gite ~1013 8) ato P2(B] (28: 108 Ba} aya ‘A 10 Pafbar } (1-2 * 102M) HOBr + OCr = = HOCL + OBr> Ky = 1/15 HOC] == Ht + OC Ky = 3.0x10% HOBr SHY + OBr K=KjKz = 2.0% 10% (a) Decrease (b) give off (c) negative (59.0 103 J/mol/(8.314472 s(K-mol)\298.15 K) = 5 x [Ott (a) Right because reactant is added (b) Right because product is removed. (c)_ Neither because solid graphite does not appear in the reaction quotient (d) Right, The pressure of reactant and product both increase by a factor of 8. However, reactant appears to the second power in the reaction quotient and product only appears to the first power. Increasing each pressure by the same factor decreases the reaction quotient. (ec) Smaller. An exothermic reaction liberates heat. Adding heat is like adding a product. 5334 6-10. 6-12. Chapter 6 @) K= Pigg = CAGUT = (AP ~ TASVRT = er Hl(63.11 * 103 Jmol) ~ (298.19K)(148 J K-F mot Y(8.3 14 J K+ mote !(298.15 K)} = 4.7% 104 bar (b) Py0 = 1 = eA-TASYRT => AHP — TAS? must be zero. 7 2 AR _ = 153% AH ~ TAS? = 0 => T= Qe = 426K = 153°C (a) Let's designate the equilibrium constant at temperature Tj as Ky and the equilibrium constant at temperature 72 as Kp. RT) == gM = TAS RT] = e~AN'IRT) « gAS'IR Ky) = Similarly, Kz = e~AWIRT2 « gAS'IR K Fe Dividing Ki by Kz gives Ge = (AN /R UT VT) Putting in Kj = 1.479 x 10° at 7) = 278.15 K and Ky = 1,570 « 10° at Tz = 283.15 K gives AH” = 47.82 kJ/mol. (b) K = e-ANRT + gAS'IR ee ast) AS. Ink = RUD) TR v mx b A graph of In K’ vs. 1/T will have a slope of -AH'/R| 48.0 Pa) ,/_1370 Pa \/_3310 Pa \ @) o-lus Pied) (oe Puber) 08 Paar } 8x 10-4 < K The reaction will go to the It was not really nevessary to convert Pa to bar, since the units cancel. (b) Hy + Bry = 2HBr Initial pressure: 1370-3310 48.0 Final pressure: 1370-x 3310-3 48.0 + 2x Note that 2x Pa of HBr are formed when x Pa of Hz are consumed. (48.0 + 7 72x 104 => x=4.50Pa 306 Pa, Pups = $7.0 PaChemical Equilibeium 58 6-15, 6-16, 6-17, 6-18. 6-19. 6-20, (©) Neither, since Q is unchanged. (d) HBr will be formed, since AM is positive. ‘The concentration of MTBE in solution is 100 jxg/mL = 100 mg/L. The molarity 0.100 g/L. ; is [MTBE] = 99-15 grmol = 1-134 109 M. The pressure in the gas phase is P = [MTBE}/Aj = (1.134 103 MY(1.71 M/bar) = 0.663 mbar: [Cur [Br] = Kop [Cu*}[0.10] 5x 10% => [Cut]=5* 108M [Ag*}'[Fe(CN)§1 = Ksp [1.0 x 10-S}4EFe(CN)E] = 8.5 x 1043 = [Fe(CN)$] =8.5 x 102!M =8.5 2 If we let =[Cu?*], then [SOF] = [Cu2*}# [OH}® [SOF] = @y4 (1.0 x 10-66 4x) 3 x 10-69 iq (423 « 10°69) 2 rele) = Eo x 106 = 3.9« 107M (a) [Zn2*P[Fe(CNYE] = (0.000 10)2[Fe(CNYE] = 2.1 « 10-46 => [Fe(CN)§] = 2.1 108M (b) [Zn2*P[Fe(CNYE| = (9.0 * 10-7)2Fe(CNYE] = 2.1 x 10-16 => [Fe(CN)E ] = 8.4% 104M BX; during precipitation of AX3. coprecipitates with AX3. This means that some BX2 is trapped in the AX3 For CaSOq, Ky = 2.4.x 105. For AgoSO4, Kap = 1.5 * 105 Removing 99% of the Ca2* reduces [Ca?*] to 0.000 500 M. The concentration of SOF in equilibrium with 0.000 500 M Ca?* is 2.4 * 10-5/0.000 500 = 0.048 M. This much SO3*> will precipitate AgoSOq, because O = [Ag*}? [S03] = (0.0300)? (0.048) = 4.3 « 10°5 > Ky, The separation is not feasible. When Ag* first precipitates, [SO%] = 1.5 * 10°5/(0.030 0)? = 1.67 « 102 M. [Ca2*] = 2.4 * 105/1,67 * 10-2 = 0.0014 M. 97% of the Ca?* has precipitated. BaCrOy(s) = Bat + CrOY — Ky = 2.1 « 10-l0 AgyCrO,(s) = 2Ag’ + CO} Ky56 6-21. 6-22, 6-23. 6-24. Chapter 6 The stoichiometries are not identical, so it is not clear that the salt with lower Ksp Will precipitate first. Let’s try each possibility. Suppose that BaCrOg precipitates first. The concentration of CrO% that will reduce Ba?* to 0.1% of its initial concentration is [Ba2*][CrO%}] = [1.0 * 10° 110-10 => [CrO%] Will this much chromate precipitate 0.010 M Ag*? We test by evaluating the reaction quotient for AgyCrO4: Q = [Ag*P[CrO%] = (0.010)2(2.1 * 10-5) = 2.1 « 109 > Kep for AgaCrO4 Since Q> Kyp for AgyCrO4, Ag* will precipitate. Let’s try the reverse calculation. [f Ag7CrO4 precipitates first, the concentration 5M is 2.1% 105M, of CrO¥ that will reduce Ag* to 1.0 « 1 [Ag*P[CrO3] = [1.0 x 10°5}2{CrOF] = 1.2« 10-12 = [CrO%] = 0.012M. This concentration of CrO% exceeds the concentration required to precipitate 99.90% of Ba?*, Neither Ag* nor Ba2* can be 99.90% precipitated without precipitating the other ion. Salt Kep AgCl 1.8% 1071 Kop 10.10 18 «104 AgBr 5.0% 10-13 Kp 10.10 5.0 x 19-12 Agl 8.3% 10°17 Kp 10 = 8.3 10°16 AgCrO, 1.2 10-12 a)Ksp/0.10 3.5.x 106 F- requires the lowest concentration of Ag* to begin precipitating, so [- precipitates ion is: I” before Br" before CI’ before CrO’ first, The order of precipi At low I’ concentration, [Pb?*] decreases with inere ing (17) bee: reaction Pb2* + 217 —» Pbl2(s). Concentrations of other Pb2*~ I" species are negligible. At high I concentration, complex ions form by reactions such as Poi(s) + F > Poly. (a) BF; (b) Asks [SnClo(aq)] [Sn*ICrP = Bo => [SnCl2(aq)] = B2[Sn2* {C1}? = (12)(0.20)(0.20)? = 0.096 MChemical Equilibrium 57 6-25. 6-26, 6-27. 6-28. 6-29, [Zn2*] = Kyy/[OH"? = 203 x 103M [ZnOH*] = By[Zn2*] [OH'] = B)Kep!fOH'] = 9 = 10M [Zn(OH)2(aq)] = B2[Zn2*] [OP = B3Ksp [OH] = 6 x 10°°M [Zn(OH)3] = fs[Zn2*] [OHS = 3Ksp [OH] = 8 x 10°°M [Zn(OH)3] = BylZn2*] [OH]! = ByKsy [OHP = 9 x 10-14 M Nat + OH = NaQH(aq) Initial concentration: 1 1 0 Final concentration: lax 1- : Toe 02 SF 015M x = 0.2-O4x+0.2x7 0.212 1.4y +0.2 = 0 @ be _ bah? —dac _ 14 efi? 40.202) aaa 2a 7 2(0.2) = 6.85 or 0.15 | or formal concentration of NaOH), so the % of the sodium is in the form NaOH(ag). xcannot be greater than 1 (the correct answer must be 0.15. That Ry Pbin(s) = Pb? + 2 Koy > [Pb2*T[IP = 7.9 109 Bo Pb2* + 21 & Pbin(ag) Bz = [Pbla(aq)] / [Pb2*][F-]2 = 1.4 x 103 Pbin(s) = Pbla(ay) KK = KepB2 = 1.1 * 105 = [Pblo(aq)] Lewis acids and bases are electron pair acceptors and donors, respect OCH) F3B + :O(CHs)) > F Lewis Lew! acid base Adduet Bronsted acids and bases are proton donors and acceptors, respectively: HS + © O > (OH + Hs” Bronsted Bronsted acid base (@) Anadduct (b) dative or coordinate covalent © conjugate (a) [1] > [OU]; [OH] > (Hy58 6-30. 631. 6-32. 6-33. 6-34, 6-35, 6-36. 6-37. 6-38. Chapter 6 vith water to form to exclude CO>, Dissolved CO> from the atmosphere lowers the pH by reacti carbonic acid. Water can be distilled under an inert atmosph or most CO2 can be removed by boiling the distilled water SOp in the atmosphere reacts with moisture to make H2SO3, which is a weak acid, HaS03 can be oxidized to HSO4, which is a strong acid H 1 i H-c -H OH yooo4 There is no place for OH to HC Nt 0-H bond to (CH3)4N 4 | 4 H-C-H 4 (a) HI (b) H20 2H2S0, = HSO3 + HySO} acid base (@) H30* 10 @) H3N CH9CH2N Hy HN CH)CH2NH2 (b) CeHsCOnH CoHsCO3 (b) CsHsNH™ IsN (@) [H*] = 0.010 M = pH = ~log[H*] ~ 2.00 (b) [OH"] = 0.035 M => [H*] = Kye / [OI] (©) [H*] = 0.030 M = pH = 1.52 @) [H"] = 3.0M => pH =-0.48 (©) [Oi] = 0.010M = [H*] = 1.0* 10-'2M => pH = 12.00 6 10°13 M => pH = (@) Ky=[H'] (OH) = 1.01 « 10-4 at 25°C x2 = 1.01 x 10°14 = x =[H*] = 1.905 x 10-7 M => pH =—Iog H'] = 6.998 (b) AL 100°C, pH = 6.132 Since [H*] [OH] = 1.0 10-4, & = [14 (ON = 1.0 x 1056Chemical Equilibrium 39 6-39. 6-40. 6-41. 6-42. 6-43. 6-44, 6-45, 6-46. 6-47. 6-48, [La3*] [OH = Kop =2 = 10°21 [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, RCO2H R3NHtX” Mr" Weak acids: Carboxylic ‘Ammonium Metal acids ions ions : RCO;M* R3N 3 Weak bases: a rsineg Carbonylate ions CxCCO2H = ChhCCOz + H Orns = Ours +H Lad} + H)O = LaQH?* + HY + ' (ON = 0 == (COs + or HOCH2CH2S" + H20 = HOCH2CH)SH + OH” HCO; = Ht + COZ Kip: HCO}* H2O F H2CO3 + OFF (a) H3NCH)CH)NH3 HaNCH2CHNH3 + Ht WE WE HaNCH,CHNH3 H)NCH CH)NH2 + H* yas . Ke z zl (b) “O2CCHCO} + H{O = — HOACCHACO} + OF Khe HOCCH2CO; + 10 S HOZCCH2COH + ON (a), ©) Kw - CN + HhO F HCN + OH Ky = = 1.6% 10560 6-49. 6-50. 6-51. 6-52. Chapter 6 Ke Kg HPO, = POF + He HC203 + HO = HyC204 + OFT Ky = B® = 704% 103 Ka = BY 6.25% 108 al * Kis x a2 2. Ky = ot = 43x 108 Ro 7 43% 10 Add the two reactions and multiply their equilibrium constants to get K = 29% 106. {a) Ca(OH), (s) Ca? + 20H XOX = Key = 10519 => v= 1.2% 102M (b) Since some Ca2* reacts with OH" to form CaOH"*, the Ksp reaction will be drawn to the right, and the solubility of Ca(OH)p will be greater than we would expect just on the basis of Kp, Reversing the first reaction and then adding the four reactions gives Ca2* + COx(g) + H20() = CaCOx(s) + 2H* K = Keo 3K 1K2/Ksp K = G4 1024.5 « 10-79(4.7 x 106.0 x 10-9) = 1.2 x 10°10 LP 8x10 ge 19x get {Ca?*JPco, ~ [Ca?*][0.10} A [Ca2*] = 2.7% 103M = 0.22 9/2.00LTL. 72. 7-4. 15. 7-6. 7-10. CHAPTER 7 ACTIVITY AND SYSTEMATIC TREATME! OF EQUILIBRIUM As ionic strength increases, the charges of the ionic atmospheres increase and the net ionic attractions decrease. There is less tendency for ions to bind to cach other. fa) true (b) true (c) true (a) ${0.0087- 12 +0,0087-(-1)2] = 0.0087 M (b) $ (0.0002 - 32 + 0.0006-¢-1)2] = 0.0012M (a) 0.660 (b) (c) 0.18 (Ex3* isa lanthanide ion) (d) 0.83 The ionic str Therefo y = 400.914 + 0.86) = 0.887 h 0.030 M is halfway between the values 0.01 and 0.05 M. ficient will be halfway betw the activity c }0n/0.083 / 305) 31 L + (601 3 = 0.05 If fether(ag)] becomes smaller. ye¢her must become larger, since KE [ether(ag)] ¥ g¢yye) 18 @ Constant The solubility of HgoBr i Br to 0,001 00 M KBr. mall, so we assume that Hg2Brz contributes negligible Ht = 0.00100 M, [Br] =0.001 00M. ¥4, = 0.964 Kop = 5.6% 103 = [} [Br- "8 Mug? }(0.867}(0.001 00)2(0.964)2 => [Hg¥'] = 7.0 « 10-17 M Cheek our assumption: Yes, Br from Hg2Br2 is negligible, The solubility of Ba(IO3)2 is small, so we assume that Ba(IO3)p contributes negligible Ty" to 0.100 M (CH3)NIO3, 6!TAL 7-12. 7-13. 7-14. Chapter 7 H =0.100M, [103)]=0.100 M, 7,,2+ =0.38, 710; = 0.775 Kop = 1.5% 109 = (Ba?*] 25 [10327 1; = [Ba?*](0.38) (0.1007 (0.775)? => [Ba?*] = 6.6 107M. Ionic strength = 0.010 M (from HCl) + 0,040 M (from KCIO4 that gives K*+C10j) = 0.050M. Using Table 7-1, 74 = 0.86. PH =-log (H*]¥,,+ = -log[(0.010)(0.86)] = 2.07. Ionic strength = 0.010 M from NaH + 0.012 M from LiNOs = 0.022 M. Interpolating in Table 7-1 gives Yoy- = 0.873. K 1.0 « 10-14 Hy = ——“— = Ogingoaty = blS* 102 (He [ONT Yj ©.910K0.873) PH = slog(1.15 « 10-17) = 11.94 Uf we had neglected activities, pH ~ —log[H*] = 12.00 9,185 @-A6 * 10 15-293.15) = 69.474 5 « 106y[(69.474) (323.15)]}-9/2(-2)2-Y0.100 2 400 -J0.100 2.00 J(69.474)S23.15) 0.329 (Inthe table, y= 0.355 at 25°C.) Spreadsheet for Debye-Hiickel calculations Pe: B c D E T [Tonic strength [Gamma =n [Gamma Ga) [Camm Goo) [Gamma @=a | 2 0.0001 98S 0.955 0901 0831 3 0.0003 0.980 0924 0.836 0.127 4 0.001 0.965 0.867 0.733 0.565 5 0.003 0.942 0.787 0.583 0383 6 0.01 0.901 0.660 0393 0.190 7 0.03 asd7 o515 0.2: 07 cep O41 0.769 0350 0.094 0.015 9 1 | B2 = 10 OST*SgrAD Cl -OOSqAEADVIOSY 1 [C2 = 104-0514 Sqrt( A214 400"SgrtA2/305)) 12. [ Dz= 10° CO.STFO*Sqrt AIVCLAON"SgrtA2V3O5)) 13, [ED = 10°V-0.51°16*Sqrt/A2V{1-400"Sqr(A2V305))Activity and Systematic Treatment of Equilibrium 6 TAS. 7-16. 0.8 06 0.4 Activity coefficient o2 0.0. > 0001 004 o1 A lonie strength (M) The equilibrium constant is [ATva- [HATHA From the table of activity coefficients, yyy: = 0.83 and ya- = 0.80 at p= HA SHY +A: For HA, we estimate log ya = Aue = (0.20.1) = 0.02, or ya = 1002 = 1.05, Putting activity coefficients for jt = 0.1 M into the equilibrium expression gives WT (ATa- _ [H*](0.83)[A100.80) _ 0.63 HUA Ky = is (HA}Ha, [HA](1.05) [HAT HA or “THAT (HOLM) = Ky0.63 The activity coefficients at x =O are all 1, so the equilibrium expression is (CHM [Ndva: _ (HA(DEA TC) _ [HAYA =0 [HAlvas (THAI) Ay =O The concentration quotient at the two different ionic strengths is HA (HAy (#70) HAO Concentration quotient = in agreement with the observed value of 0.63 + 0.03. The charge balance states the magnitude of positive charge equals the magnitude of negative charge in a solution. ‘That is, the solution must be neutral. ‘The mass balance states that atoms are conserved. If'we deliver a certain number of atom A. into a solution, then the sum of atom A in all species must equal the atoms of A64 7-22. 7-23. 7-24, 7-25, Chapter 7 delivered to the solution. If we deliver a certain ratio of atoms A and B into the solution, then the sum of atoms of A and B in all species must be in that same ratio. Charge and mass are proportional to molarity, not to activity, (H*] + 2[Ca?*] + [Ca(HCO3)"] + [Ca(OH] + [K*] = {OH"] + [HCO5] + 2[CO%] * [C104] Charge: [H*] = [OH"] + [S03] + 2[80}] [H*] = [OH] + [H2AsOj] + 2[HAsO}] + 3[As0%] H-O (a) Charge balance: 2[Mg2*] + [H*] + [MgBr*] + [MgOH*] = [Br] + O87] Mass balance: total Br = 2(total Mg) [MeBr*] + [Br] = 2{(Mg2*] + [MgBr*] + [Mg H}} (b) [Mg?*] + [MgBr*] + [MgOH*] = 0.2M (MgBr*] + [Br"] = 04M 250 mL of 1.0 < 10° M charge = 5 * 10° moles of charge. coulombs mole of charg (0.25 * 10 moles of el = 0.024 12C. 9.648 » 104 The dielectric constant of air is = | and the separation is 1.5 m. 024 12) (0.024 12) (52) (2.3 « 106 N) (0.2248 pounds/N) = 5.2» 105 pound: Two elephants do not weigh eno = 23x 106N, 0. Force = -(8.988 « 10%) { to keep the beakers apart [CH3CO3] + (CH3CO2H] = 0.1M 2 Xett 2D2YF HPQ} SPO} (Y2] = EQYz'] + 2payty Yrotal (22QV3'T+ 22X2¥4*]+ 2203} 3 (total Fe) = 2 (Lotal sul fur) 3 {[Fe3*] + [Fe(OH)?*] + [Fe(OH)5] + 2[Pe2(OH)$'] + [FeSO4]} 24{FeSO}] + [SOF] + [HSOj)} Fex(OH)}" contains 2 Fe. We write 2 in front of [FexXOH)'| bee:Activity and Systematic Treatment of Equilibrium 65 7-26. fa) (>) Pertinent reactions: _ HAN alOH K A+HO = HA+OH Kp 5.7x 1010 (A) (ATYa- Kw HO = Ht+ OH Kw = (Hl (OM Toy = 1.0% 104 (B) Charge balance: [H*] + [Na"] = [OH] + [A] © Mass balance: [Na"] = 0.01M = F (0) Mass balance: [HA] +[A’] = 0.01M = F «© Now we neglect activity coefficients. We will make the following substitutions in the charge balance [OH] = K/fH'] From Equation A: [HA] a ® From Equation E: [HA] = F~[A'] @ Now equate the expressions for [HA] from Equations F and G to solve for (A’] F-[A] [OH] feiKgeeetEyE 4 _ FIO wont) -F = (AT = OH] Now substitute K«/[H"] for each [OH] in the equation above to get 4. FKWIH FR {A} = RK) ~ Kel) + Re a) We can now substitute for all terms in the charge balance using [A’] from Equation H, [OH] = Kw/{H"], and [Na"] = F: Charge balance: [H*] +[Na‘] = [OH] +[A] i Ky FKy (+E = ey? RPT + Re o Equation I has the form we were looking for. The only unknown is [H*]. For convenience in finding a numerical solution, | will rearrange as follows: Ky FKy - 08 ny? RI] =K EPI -F o ‘The following spreadsheet evaluates the right side of Equation J in cell D9. Guess a value for [H"] in cell B7. Before using Goal Seek in Excel 2007, click the Microsoft Office button at the top left of the spreadsheet, click on Excel Options, and then on Formulas. Set Maximum Change to te-14, In earlier versions of Excel, go to Tools and Options and select the Calculations tab and set Maximum change to le-14. ‘Then execute Goal Seek to vary [H"] in cell B7 until the sum in cell D9 is close to 0 (within 1e-14), The answer in cell B7 is[H"] = 4.19 x 10° M or pH = 8.3866 7-21. Chapter 7 Cells C15:C17 compute other concentrations from the relations Ku 2 Fy Kil A [OH] = aay (A] = RUrTe Re (HAI = Thi A B c D E Finding the spacies tn NaOAc Solution Using GOAL SEEK to Solve for (H’] 1,00E-14 Ky = Ky= 5.70E-10 Fe 0.01 (Guess for (H'}= 4.195-09 pH=-logH]= 8.38 KoAH] + FK M(H") + K,)(H']- F = 1 AEAG 1 Tools --> Options --> Calculation -> Maximum change = 1e-14 12 Use GOAL SEEK to vary [Hin cell B7 until the sum in 3, cell D9 is equal to zero 14 15 16 7 [OH] =K,/(H"} = 2.396-06 A] = FKAKa(H"] + Ky) = 1.008-02 [HA] = KAVIOH] = _2.398-06 fa) (b) Pertinent reactions: Ky CalOly{s) =P Ca2*+ 20H Key = [Ca?*Tyeq2lOWP rg. = 6.5 * 10-6 [CaOH*Wewon Ky ‘ae - = CaOH* Ki = Ca2* + OH: = Cal 1 [Ca Tea OH} 2.0 * 10! Tow tho & w= 08 Ky = [Hyg (OH Tope = 1.0 x 10-4 Charge balance: 2[Ca?*] +{CaOH*] + [H*] = [OFF] Mass balance: [OH"] + [CaOH*] = 2¢[Ca2*] + [CaOH*}} + [HI] species containing OH" species containing Ca?* (Mass balance gives the same result as eharge balance.) There are 4 equations (3 equilibria and charge balance) and 4 unknowns: [Ca?*], [CaOH*]. [H*], and [OFF]. The approximations we make are to disregard the activity coefficients and to t [H*] in the charge balance because [H*] << [OH] in basic solution. ‘The charge balance becomesActivity and Systematic Treatment of Equilibrium 67 2{Ca?*] + [CaOH*] = [OH] (A) Substituting [CaOH*] = Ky[Ca2*][OH] into (A) gives lon] __ [OH] Substitute this expression for [Ca2*] into the solubility product: *OHP ren (B) [Ca¥] + Ki[Ca?* [OH] = [OH] > [Ca?*] Ksp We solve Equation B in the spreadsheet by guessing [OH] in cell C4 until the expression in cell D4 is equal to Kep. We used Goal Seck for this purpose. A_ 1B c D ] Ca(OH), solubility Kop [[OHTyoose= _ [OHT/(2 + KOH) = 65E-06 00253525] E.5000E-05 Kye | 2.06401) [[Ca*]= [CaOH']= asiori26: 10081276 KOH] = 3.94E-13 1493 /(2 + ABCA) iH Results: [Ca?*] = 0.010 1M [CaOH*] = 0.005 1M {OH-] = 0.0254M (H*] = Ky/[OH] = 3.9.x 10-13M Total disselved Ca= 0.010 | + 0.005 1 = 0.0152M ‘The formula mass of Ca(OH); is 74.09 g/mol, so 0.015 2 M is 1.13 g/L. The Handbook of Chemistry and Physics lists the solubility of Ca(OH)2 as 1.85 at 0°C and 0.77 g/L at 100°C. 7-28, (a) Pertinent reactions: Zn + SOY = ZnSOslaq) Kion pai [ZnSO4taq)] tra? MSO NSO [zn2 (zago, = | because the ion pair is neutral) Ky 1,0 = H+ OH Ky = [H hype LOM oye = LO x 10-1 Charge balance: 2[Zn2*] + [H*] = 2[SO74] + [OH"] Mass balance: 0,010 M = [Zn?*] + [ZnSOg(aq)] 0.010M= [so¥] + [ZnSOslaq)] 5 equations and 5 unknowns: (Zn2*]. [SO%]. [ZnSOg(ag)]. [H*]. [OH"]68 (b) (e) Chapter 7 Since there is no coupling of the zine sulfate and water equilibria, [H*] = [OH] = 1.0 10-7 Mand we can disregard H* and OF in this problem Substituting [ZnSO4(aq)] = 0.010 ~ [Zn2*] and [SO% ] = [Zn?*] into the ion pair equilibrium expression gives . [ZnSOs¢ag)] Kion paie= San ee [Zn?*}izq2*(SO% Wgo%y 0.010 ~{2n2*} (Zn? 77 q241Z0? Hyso3 Kion aie™ Rearranging gives (220)[Zn**Pr7424I50%7 [Zn2*] - 0.010 = 0. (A) Setting Yzy2* = gor = | allows us to solve quadratie Equation (A) to find [Zn?*] = 4.84 « 103M. Ionic strength = H([Zn2"]-4 + [S03] -4) = 0.0194 M Interpolation in Table 7-1 gives 772+ = 0.630 and ygq2- = 0.609. Putting these values of y into Equation (A) gives [Zn2*] = 6.47 x 10°7M 3° iteration: pt = 4 (6.47 x 103) = 0.0259 M 0.599 Yoq2- = 0.574 [Zn2*] = 6.65 x 103M. tag? S03 ath iteration: jt = 0.0265 M Yat = 0596 ygo% = 0571 [Zn2*] = 6.67 «103 M 0.010 ~ 6.67 « 10 Ton-paired percent = ———gjq—— * 100 = 33% fonie strength = 4 (6.67 x 10°3) = 0.027M Acid hydrolysis: Zn2* + H20 Z2n0H* + HE & >. K 7 Base hydrolysis: SOy + HO = HSO3 + OW Appendix I gives the formation constant (/4) for ZnOH* We can find K, for Zn” by adding the f; reaction to the Ky reaction: > Ay s Zn2* + OH = ZnOH = 10°" Ky 40 = HY + OH Zn + HO = ZNOH* + HY Ky = fiw = 10"Activity and Systematic Treatment of Equilibrium 69 7-29, The base hydrolysis constant for SOF is Kw/Kyo for HsSOx: u soy +H" = iol” q =" HSO} K HO = Ht + OF = geo - x SO% + HO = HSO)+ OH Ky=Ku/Ku= 102" Pertinent reactions: LiF(s) = Li’ + F Kop =(Li*Ty (+ [Fyge = 0.0017 LiF(s) = LiF(aq) Kion pair = (LiF(aq)}ypip = 0.0029 Ky 4,0 = HY +OH- Ky = [H*lye* (OW Woy = 1.0 10-4 Charge balance: [Li*] + [H*] = [F-]+ [OH] Mass balance: [Li*] + [LiF(ag)] = [F'] + [LiF(aq)] There are five equations and five unknowns: [Li*), [F"], [LiF(aq)], [H*], and {OH"]. There is no coupling between the LiF reactio water, so [H*] = [OH] = 1 10-7 M. [H*] and (0) leaving [Li*] = [F]. Also, the ion-paiting equilibrium constant tells us that [LiF(ag)] = 0.002 9 M with the good approximation that yy jp = 1. All that is left is to find [Li*] and [F] from the solubility product with the condition [Li*] = [F'] (Lith Fy “iteration: Let y= yp = = [Lit] =[F ] =/Kip = 0.041 M 2nd iteration: = 0.041M => y,,+=0.843 and y, = 0.824 UF Da [Rept gp = 0.049 M 3rd iteration: = 0.049 M => 7, + = 0.834 andy, = 0.812 = [Lit]=[F1=4/Rap, yp = 0.050 M 4M iteration: 4=0.049M => y, += 0.833 and y, = 0.811 and the dissociation of J caneel in the charge balance, = [Liy=—F = [Li = [Lit]=(F]=4 [Kept Ye = 9-050 M70 7-30. Chapter 7 (@ CaCO3(s) = Ca + COF Kep = 4.5 « 10-9 COx(aq) + HyO = HCO; + Ht Ky =446 «10-7 CO} + Ht = HCO} LK = 1/(4.69 x 10-11) CaCOx(s) + CO2(aq) + FRO = Cae* + HCO} K = Key Ki 1 Ka =4.2g* 105 (b) (c) The equilibrium constant for the net reaction is {Ca?* [HCC {CO2xaq)} We can substitute into this equation [HCO3 ] = 2[Ca?*] and [CO2(ag)] = Kc02PCo2 (where Kez = 0.032 and Peoy = 3.8 * 10-4 bar) to get Ca2*Y2fCa2*)2 _ eaaen Bae ReoxPco) > K => (Ca?*] =5.07 « 104 M = 20 mg/L = K =4.2¢x 105 Ie{Ca2*] = 80 mg/L = 2.0 x 103 M, then Ca2*1021Ca2*)?2 Poo, = Keogk 7 0.023 bat The partial pressure of CO> in the river is about (0.023 bar)/(3.8 * 10-4 bar) = 60 times higher than the atmospheric pressure of CO, There must be a source or inflow of ground water that is ‘of extra CO3 such as respiration in the riv very rich in CO> and not in equilibrium with the atmosphere.BL. 8-4. CHAPTER 8 MONOPROTIC ACID-BASE EQUILIBRIA HBr (or any other acid or base) drives the reaction H20 = H* + OH" to the left, according to Le Chatelier's principle. If, for example, the solution contains 104 M HBr, the concentration of OH of H¥ from HO must alsa be 10-10 M, m HO is Ky/[H*] = 10-10 M. The concentration nce H* and OH" are created in equimolar quantities. (a) pH = tog [H*] = log (1.0 * 103) = 3.00 (b) FHP] = Ky OH] = (1.0 » 10-M4y(1.0 « 102) = 1.0 10-12 M pH = —log [H*] = 12.00 ch balance: (H*] = [OFT] + (CIO, ] => [OH] = [H*] 5.0 108 Mass balance is the same 1e balance. Equilibrium: (H*] [OH] = Ky [HJ ((H"] - 5.0 « 108) = 1.0 10-4 => [HY] = 1.28 107M pH = -log [H*] = 6.89 [OH] = Kyi] = 7.8 108M => [H4] from H20 78 = 108M c f 7.8 + 108M Fraction of total [H*] from H20 = 7397197 M 7 0-61 (a) pH tog [H" Ty) 1,092 = log (0.100) y4j* => y+ = 0.809 The tabulated activity coefficient is 0.83 (b) 2.102 = log (0.010 0)yyp> => yr = 0.79L (c) The activity coefficient depends somewhat on the identity of the counterions in solution, (a) (Opyeosi = (Oyo H Ky (b) (Op-cois H,0 = (Opeout + OH" Ky (o) Opnie Iho = Orn + OW Ky ‘ @) Opn = Opn +H K2 8-6. 8-7, 8-8. 8-9. 8-10. Chapter 8 Let x= [H*] = [A] and 0.100~x = (HAJ. ld ox = 1.00% 105 x = 9, 104M => pH = -logx = 3.00 _ TAT _ 9.95 «10 7 %= Teja 000 = 995% 103 Ky BHt = B+ Ht 0,100—x xox 0.100—x ~ a = KwlKp = 1.00 10-10 1,00 * 10-10 = x = [B]=[H"]= 3.16 106M => pH=5.50 1,59 * 10-10 (CH3)3NH* = (CH: + Ht Ky Pox x x => x= 3.09% 106 = pH = 5.51 = 3.1% 106M, [(CH3)sNH*] =F —x = 0.060M. 0.060 {(CH3)3N] = Ke HW a HA = HY + Ax Q = “Tay When the system is at equlibrium, Q= Ke. Let's call the concentrations at equilibrium [A-]p, [H*]e, and [HA].. Ifthe solution is diluted by a factor of 2, the concentrations become + [A“Je, #[H*Je,and $ [HA]e. 1 ZAI, 2[HA}e Since Q < Kay the concentrations of produets must 1 [ATL]. ‘The reaction quotient becomes O THATe $k. crease and the concentration of reactant must decrease to attain equilibrium. That means that the weak acid dissociates further as it is diluted in order to stay in equilibrium. Ky 4IA] HA HEAT Ka= ‘any =F F-x x es For F= aoe 0. 2 For 99% dissociation, «= 0,99 F => Ka = fo Rags => F = (0.0102)Ky