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2013 Chemistry Comprehensive Examination

Analytical Chemistry Part

Dr. Mario B. Capangpangan, Ph.D.

Examiner

Instructions:
a. Please go to the CR before beginning the exam. Going to the CR during the exam is
forbidden.
b. Use real or scientific calculator. Cellphones are not allowed as calculator.
c. Please surrender all cellphones to instructor or proctor before taking the exam.
d. Write all scratch works in the supplied paper. Outside papers are not allowed.
e. Encircle all final answers.
f. When finished, submit all final answers and scratch works inside the provided
brown envelop. Separate the scratch works and final answers with the provided
paper clips.
GOOD LUCK!

1. Trace Concentrations. Trace concentrations are used in expressing concentrations

of different pollutants in the environment and are usually given in smaller units,
such as parts per thousand, parts per million, or parts per billion. These are
calculated in a similar manner to parts per hundred (%).

a) Table 1, when completely filled up, shows the different units for expressing
trace concentrations. Complete the table with the required information. Choose
your entries from the given terms (units) below the table. (Reproduce the table in
exactly the same format in your answer sheet).

Table 1. Common Units for Expressing Trace Concentrations

Concentration Abbreviation Wt/Wt Wt/Vol Vol/Vol

Parts per million ppm ______ or ______ or ______ or

______ ______ ______

Parts per billion ppb ______ or ______ or ______ or

______ ______ ______

Choices for table entries:

µL/mL; pL/mL; nL/mL; µg/L; ng/g; µg/mL ; µg/g; uL/L; µg/kg; nL/L; mg/kg;
ng/mL; mg/L; µg/mg; mg/mL,

where
mg = milligram; kg = kilogram; µg = microgram; ng = nanogram; L = liter; mL = milliliter;
µL = microliter; nL = nanoliter; pL = picoliter = 10-12 L
.
b) Conversions. Fill the blanks with the values that will make the relationships
correct:
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b1) 1 ppm = ______ %

b2) 1 ppb = ______ % = ______ ppm

c) If a 25.0-µL serum was analyzed for glucose, and found to contain 0.0267 mg,
what is the concentration of glucose in ppm? Only answers expressed to the proper
number of significant figures will be considered fully correct.

2. Analyte standards. A research study in environmental analytical chemistry usually

involves knowledge on correct techniques of preparation of reagents and analytes.
A research study involving a mixture of polynuclear aromatic hydrocarbons
(PAHs) as analytes is to be conducted. Initially, primary individual PAH stock
solutions (5,000-10,000 µg/mL) are to be prepared in methanol. Then, from this
stock solution, a secondary stock mixture in methanol containing all the PAHs is to
be prepared such that a spiked volume of the secondary stock mixture into a given
volume of solvent results in the desired analyte concentrations in the mixture for
the different PAHs. (Note: For all questions below, express answers to the proper number
of significant figures).

a) If a 20,000-µg/mL individual primary stock solution of naphthalene and 10,000-

µg/mL for pyrene are to be prepared (both in methanol), what weight (in
milligrams) of:

(a1) naphthalene and of

(a2) pyrene
should be dissolved in 5.00 mL of respective solution?

b) If a secondary stock mixture of naphthalene and pyrene is to be prepared from

the individual primary stock solution in (a) such that a 50.0-µL spike of this mixture
into 0.950 mL of solvent gives a concentration of 10.0-ppm for naphthalene and
20.0-ppm for pyrene, what should be the concentration (in ppm) of:

(b1) naphthalene and of

(b2) pyrene
in the secondary stock mixture?

c) What volumes (in microliters) of the individual primary stock solutions in (a)
should be used to prepare 10.00 mL of the secondary stock mixture in (b)? That is:

(c1) volume of naphthalene (primary stock solution) = ?

(c2) volume of pyrene (primary stock solution) = ?

3. Calibration curves. Most analytical methods are based on an experimentally

derived calibration curve in which a measured quantity y is plotted as a function of
the known concentration x of a series of standards. A typical calibration curve
approximates a straight line. However, because of the indeterminate errors in the
measuring process, not all of the data fall exactly on the line. Thus, the investigator
must try to derive a “best” straight line from the points. A statistical technique
called regression analysis provides the means for objectively obtaining such a line
and also for specifying the uncertainties associated with its subsequent use.
The simplest regression procedure is the method of least squares. When this method
is used to generate a calibration curve, it is assumed that there is actually a linear
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relationship between the measured variable (y) and the analyte concentration (x).
This relationship is stated mathematically as
y = mx + b
where b is the y intercept and m is the slope of the line. Also, it is assumed that any
deviation of individual points from the straight line results from the error in the
measurement (y values), i. e., no error in the x values of the points.

With the above background, consider the following problem.

The following data were obtained in calibrating a calcium ion electrode for the
determination of pCa. A linear relationship between the potential E and pCa is
known to exist:

pCa E, mV
5.00 -53.8
4.00 -27.7
3.00 +2.7
2.00 +31.9
1.00 +65.1

a) Derive the regression equation of the form y = mx + b for the least-squares line
through the points.

b) Calculate the pCa of a serum solution in which the electrode potential was +20.3
mV.

c) Calculate the:
c1) absolute standard deviation, and
c2) relative standard deviation
for pCa in (b) if the result was from a single voltage measurement.

d) Calculate the:
d1) absolute standard deviation, and
d2) relative standard deviation
for pCa in (b) if the result was from the mean of eight replicate measurements.

End of Analytical Chemistry Examination

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© Dr. MarioBC
02.12.13