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CHEM 213 Chemical Analysis Exam 1

1 __20___ (of 20) 2 __10___ (of 10) 3 __4____ (of 4) 4 __10__ (of 10) 5 __6____ (of 6)

__50__ (of 50)


110%

KEY
Name:___________________________________________ (please print)

1. Quinine may be determined by measuring the fluorescence intensity in 1 M H2SO4 solution. Standard solutions of quinine gave the following fluorescence values. concentration of quinine x (g mL-1) 0.00 0.10 0.20 0.30 0.40 Fluorescence intensity y (arb. units) 0.00 5.20 9.90 15.30 19.10 a. Calculate by the least squares method the equation of the best straight line for the calibration curve. Report you result in the form y = [m(sm)]x + [b(sb)]. (15 points) xi yi xi2 yi2 xiyi 0.00 0.00 0.00 0.00 0.00 0.10 5.20 0.01 27.04 0.52 0.20 9.90 0.04 98.01 1.98 0.30 15.30 0.09 234.09 4.59 0.40 19.10 0.16 364.81 7.64 2 2 xi = 1.00 yi = 49.5 xi = 0.30 yi = 723.95 xiyi = 14.73 xi = 0.20, i = 9.9 Sxx = xi2 (xi)2/N = 0.30 1/5 = 0.1 Syy = yi2 (yi)2/N = 723.95 2450.25/5 = 233.9 Sxy = xiyi (xi)(yi)/N = 14.73 (1)(49.5)/5 = 4.83 m = Sxy/Sxx = 48.3 b = y mx = 9.9 (48.3)(0.20) = 0.24
sr = Syy - m2Sxx N-2
sr2 Sxx

=
2

233.9 - (48.3) (0.1) 5-2


= 1.4271183

= 0.4512944

sm =

(0.4512944) 0.1

sb = sr

xi2
Nxi2 - (xi)
2

= 0.4512994

0.30 (5)(0.30) - 1

= 0.3495677309

Equation of best line: y = [48.3(1.4)]x + 0.24(0.35) b. An unknown quinine sample gave a fluorescence intensity of 10.20. Calculate the number of quinine in g/mL in the unknown and estimate its uncertainty. (5 points) x = (y b)/m = (10.20 0.24)/48.3 = 0.2062112 = 0.21 Uncertainty in x:
sr sc = m 1 M + 1 N + (yc - y)2 m2Sxx = 0.4512994 48.3 1 1 + 1 5 + (10.20 - 9.9)2 (48.3)20.1

= 0.01 g/mL The final answer is 0.21 0.01 g/mL.

2. In a Kjeldahl nitrogen analysis, nitrogen in substances such as protein, milk, cereal, and flour is determined. organic C, H, N + boiling H2SO4 NH4+ + CO2 + H2O A typical protein contains 16.2 wt% nitrogen. A 0.500-mL aliquot of protein solution was digested, and the liberated NH3 was distilled into 10.00 mL of 0.021 40 M HCl. The unreacted HCl required 3.26 mL of 0.019 8 M NaOH for complete titration. Find the concentration of protein (mg protein/mL) in the original sample. (10 points) The initial amount of HCl in the receiver was (10.00 mL) x (0.02140 mmol/mL) = 0.214 mmol. The NaOH required for titration of unreacted HCl in the above reaction was (3.26 mL)(0.0198 mmol/mL) = 0.0645 mmol. The difference , 0.214 0.0645 = 0.1495 mmol, must be equal to the quantity of NH3 produced in produced and distilled into the HCl. Because 1 mol of nitrogen in the protein produces 1 mol of NH3, there must have been 0.1495 mmol of nitrogen in the protein, corresponding to: (0.1495 mmol)(14.00674 mg N/mmol) = 2.093 mg N If the protein contains 16.2 wt% N, there must be: (2.093 mg N)/(0.162 mg N/mg protein) = 12.9 mg protein (12.9 mg protein/0.500 mL) = 25.8 mg protein/mL

3. Analysis of a sample of iron ore gave the following percentage values for the iron content: 7.08, 7.21, 7.12, 7.09, 7.16, 7.14, 7.07, 7.14, 7.18, 7.11. Calculate the a) mean, b) standard deviation and c) coefficient of variation for the values. (4 points) Results (x) 7.08 7.21 7.12 7.09 7.16 7.14 7.07 7.14 7.18 7.11 x = 71.30 Mean x = 7.13% Standard deviation, s = 0.0182/9 = 0.0020 = 0.045% Coefficient of Variation, CV= (0.045 100)/7.13 = 0.63% x-x -0.05 0.08 -0.01 -0.04 0.03 0.01 -0.06 0.01 0.05 -0.02 (x x)2 0.0025 0.0064 0.0001 0.0016 0.0009 0.0001 0.0036 0.0001 0.0025 0.004

(x x)2 = 0.0182

4. To measure the nickel content in steel, the alloy is dissolved in 12 M HCl and neutralized in the presence of citrate ion, which maintains iron in solution. The slightly basic solution is warmed, and dimethylglyoxime (DMG) is added to precipitate the red DMG-nickel complex quantitatively. The product is filtered, washed with cold water, and dried at 110 C.
H OH N Ni2+ + 2 N OH FM 58.69 DMG FM 116.12 N O O N Ni N O O N + 2H+

If the nickel content is known to be near 3 wt % and you wish to analyze 1.0 g of the steel, what volume of 1.0 wt% alcoholic DMG solution should be used to give a 50% excess of DMG for the analysis? Assume that the density of the alcohol solution is 0.79 g/mL. (10 points) Because the Ni content is around 3%, 1.0 g of steel will contain about 0.03 g of Ni, which corresponds to: (0.03 g Ni)/(58.69 g Ni/mol Ni) = 5.1110-4 mol Ni This amount of metal requires: 2(5.1110-4 mol Ni)(116.12 g DMG/mol Ni) = 0.119 g DMG because 1 mol of Ni2+ requires 2 mol of DMG. A 50% excess of DMG would be (1.5)(0.119 g) = 0.178 g. This much DMG is contained in (0.178 g DMG)/(0.010 g DMG/g solution) = 17.8 g solution which occupies a volume of (17.8 g solution)/(0.79 g solution/mL) = 23 mL

Bis(dimethylglyoximate)nickel(II) FM 288.91

5. Traces of toxic, man-made hexachlorohexanes in North Sea sediments were extracted by a known process and by two new procedures, and measured by chromatography. Method Conventional Method A Method B Concentration found (pg/g) 34.4 42.9 51.1 Standard deviation (pg/g) 3.6 1.2 4.6 Number of replications 6 6 6

a. Is the standard deviation for procedure B significantly different from that of the conventional procedure? (Ftable = 5.05) (3 points) Fcalculated = 4.62/3.62 = 1.63 < Ftable = 5.05. Standard deviations are not significantly different at the 95% confidence level.

b. Is the mean concentration found by procedure B significantly different from that of the conventional procedure? (ttable = 2.365) (3 points) Because Fcalculated < Ftable, we can use:
s12(n1 - 1) + s22(n2 - 1) n1 + n2 - 2

spooled =

4.62(6 - 1) + 3.62(6 - 1) 6+6-2 x1 - x2 spooled 51.1 - 34.4 4.13 n1n2 n1 + n2 (6)(6) 6+6 = 7.00 = 4.13

tcalculated = =

Because tcalculated > ttable (2.228 for 10 degrees of freedom), the difference is significant at the 95% confidence level.