Problems 1. Calculate the potential of 50 mL solution of 0.100M Co2+ and 0.500 M Co3+ when (a) 25.

00 mL; (b) 50.00 mL; (c) 75.00 mL solution of 0.100 M Ce4+ is added. What is the concentration of Co2+ in (b)? Given: Standard redox potential of Co3+/Co2+ = 0.855V and of Ce4+/Ce3+ = 1.610 V. 2. The concentrations of HCl and H3PO4 in their mixture are determined as following: Pipet 10.0 mL of a mixture of HCl and H3PO4 in to a 250.0 mL Erlenmeyer flask; add 2-3 drops of methyl orange, shake thoroughly and titrate with 0.100 M NaOH solution until the solution turns to yellow. Record the volume as V1 (mL). Add 3 drops of phenolphthalein and continue titrating until the solution turns to orange (mixture of pink and yellow). Record the consumed volume as V2 (mL). 1) Prove that at methyl orange end point, HCl and H3PO4 are titrated to the first protonated step and at phenolphthalein end point, H3PO4 is titrated to the second protonated step. 2) Calculate the molar concentration of H3PO4 and HCl in the mixture. H3PO4 is tripotic acid with pKa1 = 2.12; pKa2 = 7.21; pKa3 = 12.36.

Solution:

When we add NaOH, HCl will react completely, then H3PO4 will react At the first protonated step of H3PO4: pK a1 + pK a 2 pH 1 = = 4.67 2 (1) (Calculations to get this equation is shown at the end of this problem) Methyl orange changes color around this pH, so methyl orange can be used as an indicator to titrate HCl and the first protonated step of H3PO4 At the second protonated step of H3PO4: pK a 2 + pK a 3 pH 2 = = 9.79 2 (2) Phenolphtalein( P.P) changes color around this pH, so P.P can be used as an indicator to titrate the second protonated step of H3PO4. 2. If the volumes are recorded separately VHCL= V1 V2 V x 0.100 M (V1 V2 ) 0.100 M C HCL = HCL = 10 ml 10.0mL V x 0.100 M CH 3 PO4 = 2 10.0 ml . If the volumes are recorded continuously: (2V1 V2 ) 0.100 M C HCL = 10.0mL (V V ) 0.100 M CH 3 PO4 = 2 1 10.0 ml Calculation to get equation (1) and (2): At the first protonated step of H3PO4: H3PO4 + NaOH = NaH2PO4 + H2O H2PO4- HPO4- + H+ H+ + H2PO4 H3PO4 Because Ka3 is too small in comparison with Ka2, we can assume theres no dissociation of HPO4[ H + ][ H 2 A ] K a1 = (3) [ H 3 A] [ H + ][ HA 2 ] (4) [ H 2 A ] H+ ions are produced in the dissociation reaction (together with HA2- and consumed in the hydrolysis (yielding H3A), so their concentration is [ H + ] = [ HA 2 ] [ H 3 A] (5) From (3), (4), we can rewrite (5) in the form: K a2 =

K a 2 [ H 2 A ] [ H + ][ H 2 A ] [H ] = K a1 [H + ] Or after rearranging: K K [ H A ] [ H + ]2 = a1 a 2 2 [ H 2 A ] + K a1
+ Assume that [ H 2 A ] + K a1 = [ H 2 A ] ( [ H 2 A ] is sufficiently larger than Ka1 + So: [ H ] = K a1 K a 2 pK a1 + pK a 2 pH 1 = 2 Or Its similarly for calculation of pH2

2. Prove that in order to titrate 99.99% Mn+ by EDTA with the same concentration C0, the conditional formation constant should be larger than 108xC0 Solutions: Mn+ + Y4- --> MY4-n (1)
K f '= [ MY ] [ M ][Y ]

(2)

If M is 99.99% titrated, this means 0.9999 of initial Mn+ forms complex MY: [MY]= 0.9999xCM ; and only 0.01% of initial Mn+ remains in the solution as free ion: [M] = 0.01x10-2xCM If we call initial volume of Mn+ V0, since the concentration of EDTA is equal to the concentration of Mn+ ; the volume of EDTA consumed at equivalence point is also V0. Therefore at equivalence point, when M is 99.99% titrated we have:
V0C0 C = 0.9999 0 V0 + V0 2 C [ M ] = 1 10 4 0 2 [ MY ] = 0.9999

(3) (4)

Following equilibrium (1), we have: [M] =[Y] (5) Replace (3), (4), (5) into (2) leading to:
K f '= 0.9999 C0 [ MY ] 1 = = (108 C0 ) [ M ][Y ] 2 (1 10 4 C0 / 2) 2 2

4. It is possible to determine simultaneously Pb2+ and Bi3+ in the same solution as following: Pipet V (mL) of mixture solution of Bi3+ va Pb2+ in strong acidic media into a 250 mL Erlenmeyer flask. Adjust the pH of the solution to 2-3 by 5M solution of NH3. Add a little of orange xylenol indicator, shake thoroughly, solution turns to red. Titrate with

EDTA solution of known concentration (C0 M) until the solution turns to yellow. Record the consumed volume of EDTA V1 mL. Add 10 mL of acetate buffer in the solution, shake thoroughly, the solution turns back to red. Continue titrating by EDTA until the solution turns to yellow. Record the volume of EDTA consumed V2 mL. a. What are the conditional formation constants of cua PbY2- and BiY- at pH = 2 and pH =5?
K f ' = K f Y 4

* At pH = 2; Y4- = 3.4x10-14 Taking Kf,PbY2- = 1018 Kf,PbY2- = 1018 x3.4.10-14 = 3.4.104

K f , BiY ' = 10 27.8 3.4.10 14 = 3.4.1013.8

*At pH =5, Y4- = 3.7.10-7

K f , PbY ' = 1018 3.7.10 7 = 3.7.1011 K f , BiY ' = 10 27.8 3.7.10 7 = 3.4.10 20.8

b. Explain the color change during titration. Add a little of orange xylenol indicator, shake thoroughly, solution turns to red. Because orange xylenol (OX) forms a red complex with metal ions in the solutions Bi3+ + OX Bi-OX (red) Titrate with EDTA solution of known concentration (C0 M) until the solution turns to yellow. When the titration is completed, EDTA is in excess, it releases orange xylenol from its complex with metal ions, and make the solution turns to yellow which is the colour of free orange xylenol : Y4- + Bi-OX BiY- + OX (free) yellow Record the consumed volume of EDTA V1 mL. Add 10 mL of acetate buffer in the solution, shake thoroughly, the solution turns back to red. Continue titrating by EDTA until the solution turns to yellow. Similarly, since orange xylenol forms red complex with Pb2+, solution turns to red. And after the titration completes, EDTA is in excess release free orange xylenol to give yellow color. c. Whats the role of acetate buffer? Explain why by changing pH during titration we can titrate selectively Pb2+ and Bi3+ without interfering each other? Acetate buffer is added to raise the pH of solution to approximately 5. As we calculate above, at pH =2, the conditional formation constant of Bi is rather high 1014 while the conditional formation constant of Pb is quite small: 104, only Bi can be titrated by EDTA, while Pb can not. When we raise pH to 5, Kf of Pb is about 1011, large enough to allow an effective titration of Pb by EDTA.

V1 C0 (M ) V (V V 1)C0 C Pb = 2 (M ) V C Bi =

d. Derive formulas to calculate the concentrations of Bi3+ and Pb2+?

Give Kf, PbY2- = 1018; Kf, BiY- =1027.8.

5. 1.25 g of an weak acid HA is dissolved into 50.0 mL solution. This solution is titrated by 0.09M standard solution of NaOH and required 41.2 mL of NaOH solution to reach an equivalence point. Knowing that when 8.24 mL of NaOH solution is added into solution, pH of solution is 4.3, calculate the molecular mass and the acid dissociation constant of HA. (AS: MHA = 337.2; KHA = 1.26.105 ). 6. During the titration of NaOH solution 0.100 M by standard HCl solution 0.100 M at what pH would the color of solution change while using phenolphthalein as indicator? What is the titration error of using phenolphthalein as indicator? Compare with the titration error with using methyl orange? I. If we use phenolphthalein to indicate the end point, the color of solution would change at pH values within the range of 8 to 10. If we assume that the color change usually most visible at pH around pKa of the indicator, the pH at the end point could be 9.6 (any other pH within the above range also can be taken) 7. Consider the titration of 100.0 mL 0.0100 M Ce4+ in 1M HClO4 by 0.0400 M Cu+ to give Ce3+ and Cu2+. a. Write a balanced titration reaction. b. Write two different half-reactions

c. Calculate E at the following volumes of Cu+: 1.00, 12.5, 24.5, 25.0, 25.5, 30.0 and 50.0 mL. Sketch the titration curve. 8. A 3.026 g portion of a copper(II) salt was dissolved in a 250 mL volumetric flask. A 50.0 mL aliquot was analyzed by adding 1g of KI and titrating the liberated iodine with 23.33 mL of 0.04668 M Na2S2O3. Find the weight percent of Cu in the salt. Should starch indicator be added to this titration at the beginning or just before the end point? 9. A 25.00 mL volume of commercial hydrogen peroxide solution was diluted to 250.0 mL in a volumetric flask. Then 25.00 mL of the diluted solution was mixed with 200 mL of water and 20 mL of 3M H2SO4 and titrated with 0.0213 M KMnO4. The first pink color was observed with 27.66 mL of titrant. A blank prepared from water in place of H2O2 required 0.04 mL to give visible pink color. Find the molarity of the commercial H2O2. (AS: 0.5864 M) 10. You have received three shipments of uranium ore of equal weight. Analysis of the three ores indicated contents of 3.978 0.004% ; 2.536 0.003%, and 3.680 0.003 %, respectively. What is the average uranium content of the ores and what are the absolute and relative uncertainties? (5.8x10-3 %; 2x10-3%) 11. Calculate the uncertainty in the number of milimoles of chloride contained in 250.0 mL of a sample when three equal aliquots of 25.00 mL are titrated with silver nitrate with the following results: 36.78 mL, 36.75 mL, 36.82 mL. The molarity of the AgNO3 solution is 0.1167 0.0002 M.(AS: 0.0082 mmol) 12. You determine the acetic acid content of vinegar by titrating with a standard (known concentration solution of sodium hydroxide to a phenolphthalein endpoint). An approximately 5 mL of vinegar is weighed on an analytical balance in a weighing bottle (the increase in weight represents the weight of the sample) and is found to be 5.0268g. The uncertainty in making a single weighing is 0.2 mg. The sodium hydroxide must be accurately standardized (its concentration determined) by titrating known weights of high purity potassium acid phthalate, and three such titrations give molarities of 0.1167, 0.1163 and 0.1164M. A volume of 36.78 mL of sodium hydroxide is used to titrate the sample. The uncertainty in reading the buret is 0.02 mL. What is the percent acetic acid in the vinegar, and what is its uncertainty? (5.119 0.010%) 13. You are developing a procedure for determining traces of copper in biological materials using a wet digestion followed by measurement by atomic absorption spectrophotometry. In order to test the validity of the method, you obtain a NIST orchard leaves standard reference material and analyze this material. Five replicas are sampled and analysed, and the mean of the results is found to be 10.8 ppm with a standard deviation of 0.7 ppm. Does your method give a statistically correct value at the 95% confidence level? (AS: Determinate error). 14. Calcium in powdered milk is determined by ashing a 1.50g sample and then titrating the calcium with EDTA solution. 12.1 mL being required. The EDTA was standardized by titrating 10.0 mL of a zinc solution prepared by dissolving 0.632g

zinc metal in acid and diluting to 1L (10.8 mL EDTA required for titration). What is the concentration of calcium in the powdered milk in ppm? 15. Copper in salt water near the discharge of a sewage treatment plant is determined by first separating and concentrating it by solvent extraction of its dithizone chelate at pH 3 into methylene chloride and then evaporating the solvent; ashing the chelate to destroy the organic portion, and titrating the copper with EDTA. Three 1-L portion of the sample are then extracted with 25 mL portion of methylene chloride and the extracts are combined in a 100 mL volumetric flask and diluted to volume. A 50 mL-aliquot is evaporated, ashed and titrated. If the EDTA solution has a CaCO3 titer of 2.69 mg/mL and 2.67 mL is required for titration of the copper, what is the concentration of copper in the sea water in ppm? 16. Calculate the pCa of a solution at pH 10 after addition of 100.0 mL of 0.10 M Ca2+ to 100.0 mL of 0.10 M EDTA. 4 at pH = 10 is 0.35. Kf = 5.0x1010 a. What is pCa when i) 50.0 mL ; ii) 125.0 mL of 0.10 M EDTA were added into 100.0 mL of 0.10 M Ca2+? b. What is the titration error if the titration is ended at pCa = 4.7? 17. Fe3+in the solution can be titrated by EDTA as following: Pipet 10.0 mL of Fe3+ in an 250.0 mL Erlenmeyer flask. Adjust pH of the solution to 2.0. Add a small amount of sulfosalicylic acid, solution turns to violet. Titrate with standard Co (M) EDTA until solution changes color from violet to light yellow. Record volume of consumed EDTA as V0 (mL). a. Explain why the color change from violet to yellow during titration. b. Is it possible to titrate Fe3+ at pH higher than 2? c. Write down the equation to calculate the concentration of Fe3+ in the solution. 18. Calculate pBr of 50.0 mL of 0.025M KBr after addition of a. 25 mL; b. 50.0 mL; c. 75.0 mL of 0.025M AgNO3 b. The end point of the titration can be detected by using K2CrO4 as an indicator. The formation of yellow-brown precipitate of Ag2Cr2O4 signal the end of titration. Roughly estimated the titration error if 0.01M K2CrO4 solution is used. c. Explain why the titration should not be carried out too acidic or basic environment? Give Ksp, AgBr = ; 5.5x10-13 ; Ksp, Ag2CrO4 = 1.1x1012; 20. A mixture containing only KCl and NaBr is analyzed by the Mohr method. A 0.3172-g sample is dissolved in 50 mL of water and titrated to the Ag 2CrO4 end point, requiring 36.85 mL of 0.1120 M AgNO3. A blank titration requires 0.71 mL of titrant to reach the same end point. Report the %w/w KCl in the sample.