TITLE : Analyzing the Statistical Error of Physical Chemistry Experimental Data

Objectives :

1. To acquire, analyze and interpret data.

2. To demonstrate a competency and proficiency with experimental skills

involved inquantitative measurements and statistical dataanalysis.

3. To use a spreadsheet and excel statistical function to plot a graph.

Assignment 1

a. The following values were obtained for the measurement ammonium

concentration (mg/L) in a aquaculture sample :

0.403, 0.410, 0.401, 0.380

The last measurement is suspicious,should it be rejected?

Answer:

By using Q test at 90% confidence level :

�2 − �1
�=
�� – �1

x1 : the lowest value (suspicious)

x2 : the second lowest

xn : the greatest value

0.401−0.380
� = 0.410–0.380 = 0.7

The suspicious measurement, 0.380 should not be rejected because it meets the

Q test at 90% confidence level.

b. If three further measurements were added to those given in the above question

so that the complete results became :

0.403, 0.410, 0.401, 0.380, 0.400, 0.413, 0.411

Should 0.380 still be retained?

Answer :

By using Q test at 90% confidence level :

�2 − �1
�=
�� – �1

0.400−0.380
� = 0.413–0.380 = 0.606

The suspicious value, 0.380 is rejectedbecause it doesnot comply the Q test at 90% confidence level.

Assignment 2

A chemistry student wanted to measure the accuracy of the graduations

on a 400 ml beaker. The student placed the beaker on a scale accurate

to one decimal place and added water until the water reached the 400

mL line. This was repeated 8 times and recorded the following masses of

water 403.2g, 402.7g, 399.6g, 401.4g, 397.3g, 400.1g, 395.6g and 398.3g.

Assuming the density of water of is 1.00 g/ml, and by constructing a

table as shown below, calculate:

a. The mean of the measurements

 �1 + � 2 + … + ��
���� =
N

N : total number of samples

403.2+ 402.7+399.6+ 401.4+397.3+400.1+395.6+398.3

���� = 8
= 399.8 g

b. The variance of the measurements

�� − � 2
�2 =
n−1

S2 : sample variance

xi : the value of the one observation

� : the mean value of all observations

� : the number of observations

400− 399.8 2
�2 = 8−1
= 0.0057

c. The standard deviation of the measurements

�� − � 2
�=
n−1

�= 0.0057 = 0.0755

d. The standard error of the measurements

S
�������� ����� =
�
S : standard deviation
n : number of observations
 0.0755
�������� ����� = 8
= 0.0267

e. The 95% confidence limits

By using Q test at 95% confidence level :

�2 − �1
�=
�� – � 1

397.3 −395.6
� = 403.2 – 395.6 = 0.22

Assignment 3

You are to measure Ca2+ concentration associated with aerosol particles collected

onto 4 filtered samples using flame atomic absorption spectrophotometry as the

detector. You prepare 8 standard solutions for your calibration curve. The

following data wascollected :

Standard Ca2+ Solutions (ppm) Average Absorbance (A)

0.5 0.085
1 0.177
2 0.342
5 0.707
6 0.873
8 1.05
10 1.149
12 1.202
Filtered Samples Average Absorbance (A)
A 0.266
B 1.121
C 1.09
D 0.759

a. In Microsoft Excel, plot the calibration data as Absorbance versus Concentration (M units).
 (Note : 1 ppm = 0.00002495 M)

Standard Ca2+ solutions (M) Average Absorbance (A)

1.248 x 10-5 0.085
2.495 x 10-5
0.177
4.990 x 10-5 0.342
1.2475 x 10 -4
0.707
1.497 x 10-4 0.873
1.996 x 10-4
1.05
2.495 x 10-4 1.149
2.994 x 10-4
1.202

b. Define the linear region of your calibration curve. Using the trendline function, generate
the equation and standard deviation of the calibration curve for the linear region.
[Based on the graph in (a)]
c. Using your calibration curve equation, calculate the calcium concentrations (M units) for the four
samples. Remember, your calibration curve has limitations.

Filtered Samples Average Absorbance (A)

A 0.266
B 1.121
C 1.09
D 0.759

y = 0.1782 x – 0.1038

Sample A : Sample C :

0.266 = 0.1782 x – 0.1038 1.09 = 0.1782 x – 0.1038

x = 2.08 M x = 6.70 M

Sample B : Sample D :

1.121 = 0.1782 x – 0.1038 0.759 = 0.1782 x – 0.1038

x = 6.87 M x = 4.84 M
Sample Concentration (M) Average Absorbance
(A)
A 2.08 0.266
B 6.87 1.121
C 6.70 1.09
D 4.84 0.759
d. For which samples are you able to determine the calcium concentration with your calibration
curve? Which ones cannot be determine? Explain.

Sample A, B and C can be determined with the calibration curve but sample D cannot. This is
because the value of sample D exceed the limitation of the calibration curve. For example, the
average absorbance of sample D is 0.759 therefore, the calcium concentration should be within
5.0 ppm to 6.0 ppm.

e. What modifications must you do to your samples or calibration curve so that you can accurately
measure the absorbance and calculate the correct calcium concentrations for all samples?

First, increase the accuracy by increasing the number of sampling calibration. Next,
the accuracy of some methods can be improved by adding a suitable internal standard to
both calibration standards and test samples and basing the regression on the ratio of the analyte
response to that of the internal standard. The use of an internal standard corrects for small
variations in the operating conditions. Other than that, the average absorbance and calcium
concentration need to be adjusted. For instance, the average absorbance should be within 47.74
to 57.74 hence we can get the calcium concentration within 5.0 ppm to 6.0 ppm.