September 16, 2011 Exam 1 (20 pts.

Total) Name:

Introduction to Analytical Chemistry (CHM 3120 B51, Fall 2011) Signature:

Answer the following questions, showing all appropriate work and writing FINAL answer in the spaces provided. Point values for each question are given. Useful equations and tables of statistics are given on the last three pages . Make sure to read the questions carefully before attempting to answer them. You have 50 minutes. Good luck!!

1. You add 50.0 microliters (L) of a 0.100 M solution of NaCl to a 1-liter volumetric flask, and bring the final volume to 1.000 L of water. What is the final concentration of NaCl in parts per million (ppm)? Give correct significant figures. The molecular/formula mass for NaCl is 58.44 g/mol. Show all work for partial credit. (2 pt.) Answer:

2. What volume of a 100 mM solution would you need to make (by dilution) 100 mL of a 5 M solution? Show all work for partial credit. (2 pts.) Answer:

3. A Class A 50-mL buret is certified by the manufacturer to deliver volumes within a tolerance (i.e. uncertainty) of 0.05 mL. The smallest graduations on the buret are 0.1 mL. You use the buret to titrate a solution, adding four (4) successive volumes to the solution. The following volumes were added: Addition Volume (mL) 1 6.73 2 8.92 3 7.52 4 2.48 What is the total volume added, and what is the uncertainty associated with this final volume? Give appropriate significant figures. (2 pts.) Answer:

4. You are validating a method for measuring mercury in fish tissue by the method of atomic fluorescence. Which of the following pieces of information would support the ACCURACY of your method? Give all choices that apply. (1 pt.) Answer: a. b. c. d. Atomic fluorescence responses increases linearly with increasing concentration of Hg; the correlation coefficient is high (R 2 = 0.99) The concentration of Hg in a 1.000 nM Hg standard reference solution measured by the atomic fluorescence method is not significantly different (with 95% confidence) from the expected value. A spike of 0.5 nM Hg is recovered (99.99% recovery) by the atomic fluorescence method. Measure of Hg using the atomic fluorescence method conducted by three, independent laboratories provided double-blind samples of a 1.000 nM standard reference solution agreed within 0.021 nM.

5. In order to measure the amount of lead ions (Pb +) in water, you add potassium iodide (KI) which forms a precipitate of lead iodide (PbI) according to the following reaction: KI + Pb+ K+ + PbI You collect the PbI, as a precipitate from the reaction, by filtering into a pre-weighed Gooch crucible, and dry the crucible (with the collected precipitate) in a 110C oven. You determine the amount of PbI by re-weighing the dried crucible with precipitate, and subtracting the pre-determined weight of the crucible (i.e. weigh by difference). Which of the following would be expected to reduce the accuracy in your final measurement of the amount of precipitate? Give all answers that apply. (1 pt.) Answer(s): a. Not cooling the crucible properly prior to weighing it b. Handling your crucible with your hands and leaving fingerprints c. Drying the crucibles (both with and without precipitate) in an oven that consistently heats at a temperature that is 1C too high d. Using a different analytical balance to weigh the crucible without precipitate than the one used to weigh the crucible with precipitate. e. Using the same analytical balance for both weights (with and without collected precipitate), but one that consistently measures weights that are 0.010 g too high 6. You repeat the measurement described in Question 4 for a total of six times. You measure the following amounts of precipitate: 38.24 mg, 39.65 mg, 38.12 mg, 39.08 mg, 37.95 mg, 38.92 mg. a. What is the average weight measured? (2 pts.) Answer:

b. Give the 95% confidence interval for the average weight of precipitate. (2 pts.) Answer:

7. You are measuring the effects of a toxic compound on the enzyme, glutathione-Stransferase (GST), in human liver cells. You expose five (5) test tubes of cells to 100 L of a 5 ppm aqueous solution of the toxic compound (=Treated), and expose five (5) test tubes of cells to an equal volume (100 L) of water alone (Untreated). You then measure the GST activity of cells in each test tube; enzyme activity is in units of mol/minute. The following are the measurements of GST activity: Treated Tube 1 2 3 4 5 Average: Standard Deviation: GST Activity (mol/min) 3.25 3.98 3.79 4.15 4.04 3.84 0.36 Tube 1 2 3 4 5 Average: Standard Deviation: Untreated GST Activity (mol/min) 5.84 6.59 5.97 6.25 6.10 6.15 0.29

a. Is the variance of the measured GST activity of cells exposed to the toxic compound equal to that of cells exposed to water alone? Show any relevant work. (2 pts.) Yes No (circle one)

b. Is the average GST activity measured for cells exposed to the toxic compound significantly different (at 95% confidence level) than that measured for cells exposed to water alone? Show all relevant calculations, including any t-statistic. (3 pts.) Yes No (circle one)

8. The amount of chlorophyll in lake water is used to estimate the density of algae and other photosynthetic organisms living in lakes. Specifically, the fluorescence of chlorophyll can be used to measure its concentration. The amount of fluorescence is measured for the following concentrations of chlorophyll (in tap water): 1, 2, 5, 10, and 20 ppm. The results are shown in the graph below:

You also measure the fluorescence of seven (7) samples of tap water (blank), and seven (7) samples of chlorophyll in tap water at the concentration of 3 ppm. The average ( one standard deviation) calculated fluorescence for the blank was 0.0019 ( 0.0071), and the average ( one standard deviation) calculated fluorescence for 3 ppm chlorophyll was 0.9002 ( 0.0067). For concentrations of 1, 2, 5 and 10 ppm only (NOT including 20 ppm), you calculate a best fit line for the relationship between fluorescence and chlorophyll concentration with a slope (m) of 0.298 and y-intercept (b) of 0.005. The calculated R2-value for this line is 0.99. This line is shown on the graph above. This linear relationship (y=mx+b) between measured fluorescence and chlorophyll concentration is used to measure chlorophyll concentration in water. The data presented above support which of the following statements regarding the proposed method of measuring chlorophyll? Give all answers that apply. (2 pts.) Answer(s): a. The method can be used to determine unknown concentrations of chlorophyll as high as 20 ppm. b. Chlorophyll concentrations of 0.15 ppm are within the limit of quantitation (LOQ) of the method. c. Chlorophyll concentrations of 0.15 ppm are within the limit of detection (LOD) of the method. d. The use of the calibration curve, based chlorophyll in tap water, is sufficient to measure chlorophyll in lake water.

9. Which of the following directly addresses inaccuracies due to matrix effect? Give all choices that apply. (1 pt.) Answer(s): A. B. C. D. E. Use of an internal standard Spike recovery Use of appropriate blanks Following Standard Operating Procedures (SOPs) Calibrating instrumentation

Propagation of Uncertainty for Random Error: Addition/Subtraction: Multiplication/Division: ef = %ef = = (ei)2 (%ei)2 xi / n = (xi x)2 / n-1

Mean/Average of the Sample (x)

Standard Deviation of the Sample (s) Variance = s2 Coefficient of Variation (%CV) Confidence Interval: F-Test: Q-Test: =

s/x 100

= x ts/ n

Fcalculated = s12/s22 (s1 is the larger of the two variances) Qcalculated = gap/range

t-calculated (for equal variance) t-calculated = |x1 x2| n1n2 spooled n1 + n2

spooled =

s12(n1 -1) + s22(n2-1) n1 + n2 -2

Degrees of Freedom = n1 + n2 -2 t-calculated (for unequal variance) t-calculated = |x1 x2| s12/n1 + s22/n2 Degrees of Freedom = (s12/n1 + s22/n2)2 (s12/n1)2 + (s22/n2)2 n1 + 1 n2 + 1 -2

t-calculated (Paired data) sd = (di d)2 n-1

t-calculated = |d| n sd Equation of a Line: y = mx + b, where m is the slope, and b is the y-intercept Standard Deviation of a Calibration Curve: sy = (di)/n-2

sm2 = sy2n/D sm2 = sy2(xi2)/D *Note: Equation for D would be given to you. Limit of Detection: Limit of Quantitation: Standard Addition Equation(s) [X]i [S]f + [X]f = Ix Is+x LOD=3s/m S/N=3 LOQ=10s/m S/N=10

Where [X]I is the initial concentration of the unknown (X), [S] f and [X]f are the final concentrations of the standard (S) and (X), and I x and Is+x are the response of the unknown and the unknown plus the standard, respectively. [X] f = [X]i(Vo/V) [S] f = [S]i(Vs/V)

Where Vo is the initial volume of the unknown, Vs is the volume of standard added and V is the final volume (of unknown plus standard).