Chem 213, Section A0A EXAM 2 Name______Keys____________
Instructor: Dr. Sudeep Bhattacharyay
1. (points 20)
a) 6 points
Discuss the determinate error and random error with one example each (3-4 sentences
maximum in each case)
Solution:
Determinate error is defined as an error which arises from a flaw in the
measurement process. The magnitude of this kind of error remains
constant. This kind of error is reproducible.
e.g. 1. An error occurring in incorrectly standardized pH meter
2. A constant amount of error due to uncalibrated buret
Random errors are those which are due to uncontrolled variable in the
measurement process and whose magnitudes vary randomly. This lind of
error is not reproducible.
e.g. 1. Reading a scale by different persons.
2. Instrumental noise in a measurement
b) 6 points
Give an example of a chemical interference and discuss two ways to prevent it (3-4
sentences maximum for each case)
Solution:
Example of a Chemical interference: Determination of phosphorous using
molecular absorption spectroscopy in presence of Ca2+ and Mg2+.
Phorphorous is evaluated from the PO absorption band. Ca2+ and Mg2+
strongly suppresses the PO absorption. This can be prevented by the
following two ways:
a) Addition of releasing agent: Addition of TiO32- resolves the problem as
CaTiO3 and MgTiO3 are formed.
b) Standard addition method: A standard addition method can also be used
by addition of standard solution of known strength in known variable
amounts and the analyte concentration can be determined from standard
addition plot.
1
c) 8 points
Calculate the detection limit of the measurement shown in the table.
Conc Signal Intensity Std. Dev
(ppm Pb)
Blank 0 0.005
10.1 0.211 0.006
20.4 0.408 0.009
29.6 0.573 0.007
41.0 0.832 0.011
50.1 0.991 0.013
Solution:
0.832 − .211
Slope of the standard addition line = = 0.0200
41.0 − 10.1
3s 3 × 0.006
Detection limit = = = 0.900 ppm Pb
m 0.0200
2. (points 15)
In the AA analysis of Mn in river water, you prepare a series of standards to calibrate the
instrument before running the river water samples (diluted by a factor of 20). A
linear fit to standards produces a calibration curve with the equation:
y = 0.030112x + 0.000118
Statistical analysis of the calibration curve yields standard deviations for the slope and y-
intercept: sm = 1.71× 10-4 (std. dev. for the slope) and sb = 9.22×10-5 (std. dev. for the
y-intercept).
a) (3 points) Measuring 5 samples produces an average absorbance of 0.0629 and a
standard deviation of 0.00027. What is the concentration of Mn in the diluted sample
measured by the AA?
Solution:
Equation of the calibration curve y = 0.030112x + 0.000118
Mn conc. = [(0.0629 ± 0.00027) – 0.000118]/( 0.030112)
= 2.0849 ± 0.00896 units
= 2.085 ± 0.009 units (correcting the significant digits)
2
b) (9 points) Using the rules for propagation of uncertainty, find the uncertainty in the
concentration of the diluted Mn sample measured on the AA.
Solution:
Using the uncertainties of the slope and intercept the above equation can be
rewritten as
[(0.0629 ± 0.00027) - (0.000118 ± 0.0000922)]
Mn conc. =
(0.030112 ± 0.000171)
[0.0628 ± (0.00027 2 + 0.00009222
=
(0.030112 ± 0.000171)
(0.0628 ± 0.000285)
=
(0.030112 ± 0.000171)
(0.0628 ± %0.462)
=
(0.030112 ± %0.56788)
= 2.085 ± %( 0.4622 + 0.567882 )
= 2.085 ± %0.7320
= 2.085 ± 0.015 units
= 2.09 ± 0.02 units (correctin g the significan t digits)
c) (3 points) Calculate the Mn concentration and its uncertainty for the river water
(undiluted).
Solution:
Mn concentration in the undiluted water
= Conc. in the diluted water ÷ dilution factor
= [(2.09 ± 0.02) ÷ (1/20)] units
= 41.8 ± 0.4 units
3
3. (points 15) Consider a standard addition in which a V0 unit volume of a sample of
unknown initial concentration of analyte, [X]i, gives a signal intensity IX. Then a VS
volume unit of standard S (of initial concentration [Si] ) is added in to obtain signal
intensity IS+X. The analyte and the standard is the same chemical species. If [X]f, [S]f,
and V represents the final concentrations of the unknown, the final concentration of
the standard, and the final diluted volume, respectively, show that
I S+ X I [S]f
= IX + X
(V0 V) [X]i (V0 V)
(Hint: Assume that the total volume, V = V0 + VS and express the final and initial
concentrations of the analyte and the standard with V, V0, and VS)
Solution:
The intensity of the observed signal is proportional to the concentration of
the analyte. Representing the initial and final concentrations of the
unknown analyte as [X]i and [X]f and the same for the standard as [S]i
and [S]f we can write
IS+X [X]f + [S]f
= …(1)
IX [X]i
Expressing the final and initial concentrations of the analyte we get
[X]f = [X]i× (V0/V).
Replacing [X]f in eq (1) we get,
IS + X [X]i (V0 V) + [S] f [S] f
= = (V0 V) +
IX [X]i [X]i
Or dividing both sides by (V0 V) ,
IS + X [S] f
=1+
IX (V0 V) [X]i (V0 V)
Or, multiplying both sides by Ix,
IS + X IX [S] f
= IX +
(V0 V) [X]i (V0 V)
4
4. (points 15) A trainee in a medical lab will be released to work on her own when her
results agree with those of an experienced worker at the 95% confidence level.
Results for a blood urea nitrogen analysis are shown below.
Trainee: x =14.57 mg/dL s = 0.53 mg/dL n=6 samples
Experienced
worker: x =13.95 mg/dL s = 0.42 mg/dL n=5 samples
Should the trainee be released to work alone?
Solution:
1 dL= 100 mL = 0.1 L
First let us do the F-test to find out if the two s of measurements are
significantly different or not.
Fcalc = (0.53/0.42)2 = 1.59 <6.26 (df = 5 for the numerator and equal to 4 for
the denominator)
Therefore, we will conduct a T-test using pooled standard deviation
0.532 (5) + 0.422 (4)
spooled = = 0.484
6+5−2
14.57 − 13.95
6.5
tcalc = = 2.12 < 2.262 (for 95% confidence and 9
0.484 6+5
degrees of freedom)
Therefore, statistically the two results agree and the trainee should be
released.
5
5. (points 15)
a) (points 5) Draw a atom-level picture of an ion surrounded by water molecules.
Draw the presence of counter ions. Indicate the charge content of this species.
Indicate which part is described as ‘ionic atmosphere’.
(1-δ) (1-δ)
Shared by Ionic atmosphere
(–) many other
positive
charges
(–)
(–)
M+
(–)
The solvent molecules and shared
counter ions (shown in the left panel)
constitute the ionic atmosphere of
charge δ
b) (points 5) Briefly (2 sentences) explain how ionic strength influences ‘ionic
atmosphere’?
Increasing ionic strength increases the amount of ions in a solution and
consequently, more counterions surround a central ion. The charge
content (i.e. δ) of the ionic atmosphere is increased and as a result, the
net charge on the central ion gets reduced.
c) (points 5) Discuss (1-2 sentence) exactly how a buffer with high ionic strength
can prevent chemical interferences.
Since we know that the electrostatic interaction is governed by Coulomb’s
1 q1q2
law which is of the form F = , where q1 and q2 are the charges on
4πε 0 r 2
the two ions and r is the distance between their nuclii, and ε0 is the
dielectric constant of the medium, the reduction of charges (i.e. q1 and q2)
will reduce the force of attraction of the two ions. As a result, the solubility
of the analyte salt will be increased preventing the interference.
Score______/80___