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Chemistry 28 Problem set 1: 1. A sample analyzed on as-received basis for crude protein content gave a result of 45.00% .

It also has a water content of 9.85%. What is the %crude protein on a dry basis? 2. If the %Ca of a bread sample is 10.85 and 12.45 on an as-received basis and dry basis, respectively. What is the water content of the sample? Pertinent equation: %analyte (dry basis) = %analyte (as received)/(1-(%water content/100)) Manipulate this equation depending on the given information. 3. How do you classify the analysis above according to amount of analyte in #1? 4. Give an example each for water of crystallization, water of hydration and water of constitution. 5. 2.5 g KCl was dissolved in enough water and made up to a final volume of 500 mL. Express the concentration of the solution in terms of: a. molarity b. molality c. normality (KCl is used to react with AgNO3 to form AgCl and KNO3) d. %m/v e. ppt f. ppm 6. Give the ionic strength of the following 0.100 M solution of: a. NaF b. CaCl2 c. Al(NO3)3 7. Write the mass balance and charge balance equation for a system containing 0.150 M NaCl, Ba(ClO3)2 and Al2(SO4)3. Consider the dissociation of water as well. 8. Calculate the solubility of Ba(IO3)2 in a 0.033 M solution of Mg(IO3)2 by a. using activities (at = 0.1 , Ba2+:0.38, IO3-:0.77, Ksp: 1.57x10-9) b. neglecting activities (straightforward calculation of solubility) 9. Under what condition can one assume that activity is equal to molarity? 10. What is the activity coefficient of a neutral molecule? 11. Enumerate the different ways of ensuring low relative supersaturation for crystalline precipitates to form. 12. Give an example of a homogeneous precipitation system. What is its advantage(s)? 13. How are colloidal particles coagulated? What is the best way to wash colloidal precipitates? 14. During the precipitation of AgBr from NaBr where there is no excess precipitating agent (AgNO3) yet, what is the ion on the primary adsorption layer? Upon addition of excess AgNO3, what is the ion on the primary adsorption layer?

15. Name the different types of coprecipitation errors and differentiate one from each other. 16. Back titration is resorted to when the rate of reaction between an analyte and reagent is slow or when a standard solution lacks stability. The standard titrant is added in excess and then its excess amount (amount that did not react with the analyte) is back-titrated with another standard titrant. Determination of nitrogen content by the Kjeldahl method is an example of this back-tiration method. Calculate the %N in a 5.000-g flour sample analysed by Kjeldhal. After decomposition of the sample, the NH3 liberated from the sample as a result of the digestion with H2SO4 was distilled into 25.00 mL of 0.0477 M HCl. The excess HCl was then back-titrated with 5.28 mL of 0.04012 M NaOH. Calculate %N in the flour and %Crude protein (%Nx5.70). 17. What is the pH of a 0.00100 M Al(OH)3 solution? 18. A 50.00 mL aliquot of 0.0500 M NaCN (Ka of HCN: 6.2 x10-10, recall Kw= KaxKb)is titrated with 0.1000 M HCl. Calculate the pH: a. 0.00 mL reagent b. After addition of 10.00 mL acid c. After addition of 25.00 mL acid d. After addition of 1.00 mL excess acid 19. If you were to prepare a 0.100 M buffer and and a 0.00100 M buffer, which do you think will have a higher buffer capacity? Why? 20. Recall that for a polyprotic acid or base, two usable endpoints are obtained if the ratio of dissociation constants is greater than 104 (this is also valid for mixtures of acids) and if the weaker acid or base has a dissociation constant greater than 10-8. Given this, predict which of the following systems will have two usable endpoints? a. Arsenic acid, H3AsO3 Ka1: 5.8x10-3, Ka2: 1.1x10-7, Ka3: 3.2x10-12 b. Fumaric acid, HOOCCH:CHCOOH Ka1: 8.85 x 10-4, Ka2: 3.21x10-5 c. Oxalic acid, HOOCCOOH, Ka1: 5.60x10-2, Ka2: 5.42 x10-5 21. Calculate the alpha value for oxalic acid for pH 2.00 and 5.00. 22. Draw the titration plot (pH vs vol titrant) for the following titration systems: a. Equimolar amounts of NaHCO3 and Na2CO3 titrated with HCl b. Pyruvic acid , HP (Ka:3.2 x 10-3) with standard base c. Disodium maleate with standard acid (Kb1: 1.69 x10-8, Kb2: 7.9 x10-13) 23. Calculate the Ka1 and Ka2 of maleic acid from the Kb values in #22 and from Kw.