CHEMISTRY 311 - ASSIGNMENT 2

Hand-in your answers in a neat and organized format to the appropriate number significant
figures, showing chemical equations and calculations where appropriate.

Solutions
1. Calculate the relative errors associated with the propagated indeterminate readings errors
associated with the volumetric analysis of dissolved oxygen using standard analytical laboratory
glassware (100.0 +/- 0.08 mL sample, 0.0200 +/- 0.0001 N sodium thiosulfate and 5.00 +/- 0.03
mL of titrant) and compare that to the same using a digital titrator in the field (20.0 +/- 0.5 mL
sample, 0.200 +/- 0.004 N sodium thiosulfate and 80. +/- 1 digit increments).

Solution:
a) The lab based titration gives the dissolved oxygen concentration as;
(𝑁𝑆2𝑂32− )(𝑉𝑆2𝑂32− ) (0.0200 ± 0.0001 𝑁) (5.00 ± 0.03 𝑚𝐿)
𝑁𝑂2 = =
𝑉𝑂2 (100.00 ± 0.08 𝑚𝐿)

0.0001 2 0.03 2 0.08 2

𝑁𝑂2 = 1.00 𝑥 10−3 𝑁 ± (√( ) +( ) +( ) )
0.0200 5.00 100.0

𝑁𝑂2 = 1.00 𝑥 10−3 𝑁 ± (√(2.5 𝑥 10−5 ) + (3.6 𝑥 10−5 ) + (6.4 𝑥 10−7 ))

𝑁𝑂2 = 1.00 𝑥 10 −3 𝑁 ± (7.8 𝑥 10−3 ) Note: this is the relative error in the Normality (ie 0.78%)

Converting to an absolute expression of error yields, (7.8 x 10-3) (1.00 x 10-3 N) = 7.8 x 10-6 N
Thus, the propagated error in the final result is: (1.000 ± 0.008) x 10-3 N

b) The field based digital titrator method gives the dissolved oxygen concentration as;
−3 𝑚𝐿
(𝑁𝑆2𝑂32− )(𝑉𝑆2𝑂32− ) (0.200 ± 0.004 𝑁) (80. ±1 𝑑𝑖𝑔𝑖𝑡)(1.25 𝑥 10 𝑑𝑖𝑔𝑖𝑡)
𝑁𝑂2 = =
𝑉𝑂2 (20.0 ± 0.5 𝑚𝐿)

0.004 2 1 2 0.5 2
𝑁𝑂2 = 1.00 𝑥 10−3 (±√( ) +( ) +( ) )
0.200 80. 20.0

𝑁𝑂2 = 1.00 𝑥 10−3 𝑁 ± (√(4.0 𝑥 10−4 ) + (1.6 𝑥 10−4 ) + (6.3 𝑥 10−4 ))

𝑁𝑂2 = 1.00 𝑥 10 −3 𝑁 ± (3.4 𝑥 10−2 ) Note: this is the relative error in the Normality (ie 3.4%)

Converting to an absolute expression of error yields, (3.4 x 10-2) (1.00 x 10-3 N) = 3.4 x 10-5 N
Thus, the propagated error in the final result is: (1.00 ± 0.03) x 10-3 N

Note: if you convert the O2 concentration to other units (ie M or mg/L), the relative error remains
the same. Lab based: 8.00 ± 0.06 mg/L Field based: 8.0 ± 0.3 mg/L

Assign 2 2016 Solutions

2. The Method Detection Limit (MDL) can be estimated according to a procedure described in
U.S. EPA Method 300.0 by analyzing at least seven replicates with a concentration close to the
estimated method detection limit. The MDL is then calculated as (t) x (SD) where t = Student’s t
value for a 99% confidence level with n - 1 degrees of freedom and SD is the sample standard
deviation. Check for outliers at the 90% confidence level and estimate the method detection limit
for the measurements of a 2.5 ppb NO3- - N standard solution by ion chromatography.
2.8 1.7 2.4 2.9 2.1 4.0 2.3 2.6 1.8 2.7

Solution:
Applying the Q-test at the 95% confidence level, we can reject the data point 4.0.

4.0  2.9
Qexp   0.478
4.0  1.7
At N = 10, Qcrit = 0.466

Since Qexp > Qcrit, the point can be rejected.

Taking this into account,

n=9
the mean value = 2.37 ppb NO3-N
sample standard deviation = 0.43 ppb NO3-N

At the 99% confidence level, t0.01 = 3.36 (df = 8)

So MDL = t0.01 x SD = (3.36) (0.43 ppb) = 1.4 ppb NO3-N

(Note: It is customary to report MDLs to one significant figure and round up to nearest integer. Thus in
this case the MDL would probably be reported as 2 ppb NO3-N)

Assign 2 2016 Solutions

3. The analysis of cadmium by Graphite Furnace Atomic Absorption Spectroscopy (GF-AAS)
has a precision of  10 ppb based on the standard deviation obtained from > 40 replicate analysis.
A food inspection regulator has asked you to report cadmium concentrations with 99%
confidence that they are within 5 ppb of their true value.
a) How many replicate analysis would be required are required to meet this criteria?
b) How does you answer change, if you could modify the technique to lower the standard
deviation to  2 ppb?

Solution:
Since the standard deviation is based on >40 analysis, it represents a true population standard deviation ()
rather than the more familiar sample standard deviation (s).

Rearranging,

z
CI 
N

 z 
2

N  
 CI 
2
 (2.58) (10 ppb) 
a) N=    26.6
 5 ppb 

where CI = 5 ppb,  = 10 ppb and z = 2.58 at the 99% confidence level

In other words, 27 replicates are required to achieve the desired confidence interval.

b) If the methodology is refined to lower the precision to ±2 ppb, our answer is modified as;
2
 (2.58) (2 ppb) 
N=    1.07
 5 ppb 
so 2 replicates would be required to achieve the desired confidence interval.

Note the dramatic difference in the number of replicates required that results by improving the precision of the
analytical methodology.

Assign 2 2016 Solutions

4. Six replicates for the determination of zinc in an individual’s hair gave the following results
(in ppm); 2.67 2.75 2.82 3.01 2.94 2.87
a) Determine the mean and standard deviation for the results.
b) After six months of taking zinc supplements, the study was repeated. The mean value was
3.03  0.22 ppm (value  s) for five replicate samples. Is the difference between the two sets of
data significant at the 95% confidence level?

Assign 2 2016 Solutions

5. Several different alcoholic beverages were tested for ethanol content (% w/w) by two
methods, with the results summarized in the table below. Method 1 is an industry standard and
involves distilling a large volume of sample and measuring the density of the distillate. Method 2
employs an enzyme based electrochemical technique and uses only 25 L of sample. You have
been asked to review the results and assess if there is a difference in the results at the 95%
confidence level.
Method 1 Method 2
Beer A 3.82 3.80
Beer B 4.35 4.32
Beer C 3.47 3.48
Wine A 10.7 10.6
Wine B 5.83 5.90
Wine C 8.58 8.49

Assign 2 2016 Solutions

6. It is known that there is a linear relationship between the measured potential (mV) and the –
log of the molar calcium ion concentration (pCa) for calcium ion electrodes. The following data
were obtained to generate a calibration curve.
pCa E (mV)
5.00 -43.4
4.00 -17.7
3.00 12.7
2.00 41.9
1.00 75.1
a) Derive the best-fit line using the method of least squares (c.f. section 4.7, textbook).
b) Using the Excel Spreadsheet for least squares analysis described in the textbook, calculate the
standard deviations for the slope and the intercept.
c) If the electrode potential of an unknown solution was measured once as 12.3 mV, calculate
pCa and use EQN 4-27 to calculate the standard deviation in pCa. Use these results and the
information in Table 3.1 to calculate [Ca2+] and its standard deviation.

Solution:
a) E (mV) = (-29.7 mV/pCa) (-log [Ca2+]) + 102.7 mV

Calibration Curve
y = -29.66x + 102.7
R² = 0.9983
Ecell (mV)

- log [Ca2+]

b) The uncertainty in the slope and intercept are given by;

sm = 0.72 mV/pCa
sb = 2.4 mV

c) When y = 12.3 mV, the derived value of x (pCa), is 3.05  0.084

so, [Ca2+] = 10-3.05 (0.047) = 8.95 x 10-4 M

Using the formula in table 3.1(text), the relative uncertainty in [Ca2+] is given by;
sCa
 (2.3)( s pCa ) = (2.3)(0.084) = 0.19 (i.e., ~19%)
[Ca]

So, sCa = (0.19)(8.95 x 10-4 M) = 1.7 x 10-4 M and [Ca2+] = (9.0  1.7) x 10-4 M

Assign 2 2016 Solutions

7. A standard solution was prepared containing 10.0 ppm of caffeine and 5.0 ppm of an
appropriately chosen internal standard. Analysis of this combined standard gave signals for the
caffeine and internal standard of 0.155 and 0.233 (arbitrary units), respectively. Sufficient internal
standard was then added to a sample to make it 5.0 ppm in the internal standard. Analysis of the
sample yielded signals for the analyte and internal standard of 0.274 and 0.198, respectively.
a) What considerations go into choosing an appropriate internal standard?
b) Is the analytical techniques employed in this case more sensitive to caffeine or the internal
standard?
c) Report the concentration of the analyte the sample in units of ppm.

Assign 2 2016 Solutions

8. The following data were obtained in a determination of chromium in water. The protocol was
to run a blank, the sample and then the sample with two standard addition spikes. Three
replicates were measured for each sample. Calculate the mean concentration of Cr in ng/mL.
(Assume that the volume of the added spike was negligible).
Solution Conc Cr Instrument
(ng/mL) Readings
#1 #2 #3
Blank 0.00 0.005 0.009 0.003
Sample - 0.086 0.088 0.085
Addition 1 2.00 0.179 0.191 0.188
Addition 2 4.00 0.305 0.310 0.318

Assign 2 2016 Solutions

Assign 2 2016 Solutions