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)
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 ± (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
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
(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)
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
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.
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+]
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