Faculty of Natural and Agricultural Sciences Chemistry Department. Semester Test 1. Analytical Chemistry CMY 283. Time: 120 min Marks: 100 Pages: 6
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1 Faculty of Natural and Agricultural Sciences Chemistry Department Semester Test 1 Analytical Chemistry CMY 283 Date: 5 September 2016 Lecturers : Prof P Forbes, Dr Laurens, Mr SA Nsibande Time: 120 min Marks: 100 Pages: 6 Instructions: Answer all the questions. All answers (calculations, sketches, and diagrams) must be given in black or blue ink. All calculations must be shown in full. A periodic table is provided on page 5. 1
2 QUESTION 1 5 MARKS The thermodynamic solubility product K sp for AgCl(s) is at 25 C. Would you expect the concentration solubility product, K sp, at an ionic strength µ = 0.5 (obtained by an addition of 0.5 mol/l NaNO 3 ) and at 25 C, to be the same as the thermodynamic solubility product? Explain your answer and show the relationship between the two constants. QUESTION 2 12 MARKS Calculate the solubility of Ag 2 C 2 O 4 in a solutions that has been buffered to ph 9. QUESTION 3 3 MARKS Diluted NaOH is introduced into a solution that is M in Cu 2+ and M in Mn 2+. What is the concentration of the cation forming the less soluble hydroxide when the more soluble hydroxide begins to form? QUESTION 4 3 MARKS What is the [Y 4- ] of a M EDTA solution buffered to a ph of 6.00? QUESTION 5 4 MARKS A redox titration is performed using M Sn 2+ titrant, for a ml sample containing M Fe 3+.What is the potential of the system after addition of ml of titrant? QUESTION 6 8 MARKS ml of M NaCN is titrated with M HCl. a) What is the relevant chemical reaction equation? (1) b) What is the initial ph? (4) c) What is the ph after 12.5 ml of titrant has been added? (3) 2
3 QUESTION 7 5 MARKS The waste water from an industrial process contains cyanide and chloride ions, which need to be quantified by law. Could argentometric titrations be used for this purpose? Discuss and explain your answer and include a sketch showing the relevant titration curve to support your answer QUESTION 8 5 MARKS Calculate the electrode potential of a silver electrode immersed in a M solution of NaCl. E o Ag + /Ag=0.799 V, Ksp AgCl =1.82X10-10 QUESTION 9 14 MARKS What mass (in grams) of Barium iodate can be dissolved in 350 ml of water at 25 o C? Ksp of barium iodate = 1.57X10-9 QUESTION 10 9 MARKS Calculate the hydronium ion concentration in M nitrous acid. (K a for nitrous acid = 7.1X10-4 ) QUESTION MARKS What is the ph of a solution that is M in formic acid and 1.15 M in sodium formate? (K a for formic acid = 1.80X10-4 ) QUESTION 12 7 MARKS a) Name three sources of systematic errors? (3) b) Name four methods of detecting a systematic error? (4) QUESTION MARKS A g sample of a solid mixture containing benzoic acid (C 6 H 5 COOH) was dissolved and titrated with base to a phenolphthalein endpoint. The acid consumed ml of M NaOH. Calculate: a) the percent benzoic acid in the sample? b) The standard deviation of the result if: The the position of the burette can be estimated to +/-0.03 ml, A four-decimal analytical balance used that can be read at +/ g 3
4 The standard deviation of the NaOH reagent solution is +/ M The standard deviation in the molecular mass of benzoic acid is negligible Data K sp Cu(OH) 2 = K sp Mn(OH) 2 = K a1 H 2 C 2 O 4 = K a2 H 2 C 2 O 4 = K sp Ag 2 C 2 O 4 = E E o log n c d C D A a B b 4
5 STANDARD ELECTRODE POTENTIALS E 0 (Sn 4+ /Sn 2+ ) = V E 0 (Fe(CN) 3-6 /Fe(CN) 4-6 ) = V E 0 (Fe 3+ /Fe 2+ ) = V E 0 (Tl 3+ /Tl + ) = V E 0 (Tl + /Tl) = V TABLE OF DISSOCIATION CONSTANTS Acid K a (25C) Acid K a (25C) Base K b (25C) H 3 PO x 10 3 H 2 S NH 2 CONH HNO x 10 4 HC 3 H 5 O C 5 H 5 N H 2 CO x 10 7 HS NH 2 OH CH 3 COOH 1.8 x Co(H 2 O) NH HClO 3.0 x Fe(H 2 O) CH 3 NH C 6 H 5 COOH 6.3 x Al(H 2 O) CO HCN (CH 3 ) 2 NH HF C 6 H 5 NH TABLE OF SOLUBILITY PRODUCT CONSTANTS Compound K sp (25C) Compound K sp (25C) AgBr 5.0 x AgIO x 10 8 Ag 2 CO x AgI 8.3 x AgCl 1.82 x Ag 2 S AgCN 2.2 x AgSCN STANDARD AND FORMAL ELECTRODE POTENTIALS E 0 (V) 2H + + 2e - H 2 (g) Ce 4+ + e - Ce Fe e - Fe (s) Fe 3+ + e - Fe (0.700 in 1 M HCl) Sn e - Sn (s) (-0.16 in 1 M HClO 4 ) Sn e - Sn (0.14 in 1 M HCl) UO H + + 2e - U H 2 O V 3+ + e - V VO H + + e - V 3+ + H 2 O V(OH 4 ) + + 2H + + e - VO H 2 O (1.02 in 1 M HCl, HClO 4 ) 4 E E o c [ C] [ D] log a n [ A] [ B] K K [ H ] K1[ H ] K1K2[ H ] K1K2K3[ H ] K1K2K3K4 WHERE K 1 = 1.02 X 10-2 ; K 2 = 2.14 X 10-3 ; K 3 = 6.92 X 10-7 ; K 4 = 5.50 X NOTE: 4 = 2.25 X 10-5 FOR [H + ] = 1.00 X 10-6 M K K d b 5
6 6 THE PERIODIC TABLE OF THE ELEMENTS 1 H He Li Be B C N O F Ne Na Mg Al Si P S Cl Ar K Ca Sc Ti V Cr Mn Fe Co Ni Cu Zn Ga Ge As Se Br Kr Rb Sr Y Zr Nb Mo Tc Ru Rh Pd Ag Cd In Sn Sb Te I Xe Cs Ba La Hf Ta W Re Os Ir Pt Au Hg Tl Pb Bi Po At Rn Fr Ra Ac Rf Db Sg Bh Hs Mt Ce Pr Nd Pm Sm Eu Gd Tb Dy Ho Er Tm Yb Lu Th Pa U Np Pu Am Cm Bk Cf Es Fm Md No Lr
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