The hand-written hard copy of the assignment (given below) should be submitted to Lab

number 4, on or before 17-02-2023, 5.00 pm.

I. Optimization of instrumental parameters in atomic absorbance/emission spectroscopy

for maximum sensitivity: (a) Sample flow rate, (b) Flame, and (c) Background signal.

II. Numerical problems

1. The following replicate weighing's were obtained: 29.8, 30.2, 28.6, and 29.7 mg. Calculate the
standard deviation and the standard deviation of the mean. Express these as absolute and relative
values. Report this result at 95.5 % and 99.7 % confidence levels.

2. Calculate the imprecision parameters of the following set of analytical results: 15.67, 15.69,
and 16.03 mg/mL.

3. The accepted value for a substance is 24.36%. The calculated value is 24.31%. Calculate the
inaccuracy.

4. A substance was known to contain 49.10% of compound “A”. The results obtained by two
analysts using the same substance and the same analytical method were as follows:
Analyst 1: % of A = 49.01, 49.25, 49.08, and 49.14
Analyst 2: % of A = 49.40, 49.44, 49.42, and 49.42
Find out who is more imprecise and who is more inaccurate.

5. The accepted value of a measurement is 4.2 µg/g. Calculate the inaccuracy and imprecision of
the following set of values.
I: = 4.3, 4.1, 4.0, and 3.2 µg/g
II: = 4.3, 4.1, 4.0, 3.2, 4.2, 3.9, and 4.0 µg/g

6. Round off the results according to the significant figure conventions

i. 3.4 + 0.020 + 7.31 = 10.730
ii. 2.432 × 106 + 6.512 × 104 - 1.227 × 105 = 2. 37442 × 106
iii. (24 × 4.52)/100.0 = 1.0848
iv. (24 × 4.02)/100.0 = 0.9648
v. log(6.000×10-5) = -4.2218488
vi. antilog(12.5) = 3.162277×1012
vi. log(6.0000×10-5) = -4.2218488
vii. antilog(12.50) = 3.162277×1012

7. Find out the value of “y” according to the significant figure conventions.
i. y = 4.10 + 0.0050 – 1.970
ii. y =
iii. y = log [2.00 ×10-4]
iv. y = antilog[1.200]

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8. If 𝑥 , the mean of a 12 determinations is 8.37 mg, and µ, the true value is 7.91 mg, say whether
or not the result is significant if the S is ± 0.17 mg (ttab value is 2.2).

9. If SA is 0.210 and SB is 0.641 for two methods, then is there any significant difference between
the precision of the two sets of results? (Ftab value at the 95% confidence level is 2.91).

10. A new gravimetric method for the determination of iron(III) is developed. If we want to
compare this result with the reference method, the analysis is as follows.
Results of the test method: 20.10, 20.50, 18.65, 19.25, 19.40, 19.99 (% of iron content)
Results from the reference method: 18.89, 19.20, 19.00, 19.70, 19.40 (% of iron content)
Is there any significant difference between the two methods? Analyze by t test and F test.
(ttab for 9 degrees of freedom at 95% confidence level is 1.83 and Ftab value for F5,4 at 95%
confidence level is 6.26.)

11. Two different methods, A and B, were used for the analysis of five different iron compounds.
The % Fe content of the samples are given below.

Sample 1 2 3 4 5
Method
Method A 17.6 6.8 14.2 20.5 9.7
Method B 17.9 7.1 13.8 20.3 10.2

Is there any significant difference between the two methods? Analyze by t test. The ttab value at
95% CL is 2.78.

12. You are developing a new analytical method for the determination of blood urea nitrogen.
You want to ascertain whether your method differs significantly from a standard method for
determining a range of sample concentrations expected to be found in the routine laboratory. It
has been ascertained that the two methods have comparable precision. Following are two sets of
results for a number of individual samples:

Sample Your method Standard/reference method

(mg/dL) (mg/dL)
A 10.2 10.5
B 12.7 11.9
C 8.6 8.7
D 17.5 16.9
E 11.2 10.9
F 11.5 11.1

Is there any significant difference between the two methods? ttab value at 95 % CL is 2.571.

13. Find out y and Sy for the following

a. y(±Sy) = 0.50(±0.02) + 4.10(±0.03) – 1.97(±0.05)

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 ( ) ( )
b. y(± Sy) = ( )

c. y(±Sy) = log[2.00(±0.02)×10-4]

d. y(±Sy) = antilog[1.200(±0.003)]

e. y(±Sy) = 0.50(±0.01) + 4.10(±0.09) – 1.97(±0.08)

( ) ( )
f. y(± Sy) = ( )

g. y(±Sy) = log[2.00(±0.09)×10-4]

h. y(±Sy) = antilog[1.200(±0.009)]

14. Quinine can be determined by measuring the fluorescence intensity in 1.0 M H2SO4 solution.
Standard solutions of quinine gave the following fluorescence values. (i). Construct the equation
for the calibration curve, (ii). Calculate the correlation coefficient, r and comment on the value of
r. and (iii). Find out the concentration of quinine sample which gives 12.4 fluorescence intensity.

Concentration of quinine : 0.00, 0.10, 0.20, 0.30, and 0.40 µg/mL

Fluorescence intensity : 0.0, 5.2, 9.9, 15.3, and 19.1

15. Use the method of least squares to obtain the best fit straight line for a calibration curve and
calculate the concentration of ‘A’ which gives 15.4 (fluorescence intensity) for the following set
of data. Calculate the correlation coefficient, r and comment on the value of r.

Concentration of A: 0.00, 0.10, 0.20, 0.40, and 0.80 µg/mL

Fluorescence intensity: 0.0, 5.8, 12.2, 22.3, and 43.3

16. The following readings were observed during an electrochemical analysis of compound “X”.
Comment on the extent of linearity of the best fit straight line. Find out the concentration of X in
the unknown sample which gives 20.100 µA current.

Concentration of standard X (mM) Current (µA)

0.10 0.429
0.50 0.834
1.00 2.343
2.50 5.493
5.00 13.563
10.00 27.123

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17. The following ten readings are observed for an electrochemical analysis of a blank. A
standard (1.00 mM) of compound “A” gives 2.348 µA current. Find out the LOD and LOQ for
the determination of “A” in this method.

The readings are: 0.003, 0.013, 0.005, 0.001, 0.009, 0.010, 0.000, 0.005, 0.004, and 0.002 µA

18. The absorbance readings of a blank determination are 0.002, 0.000, 0.008, 0.006, and 0.003.
A standard 1.0 ppm analyte solution gives an absorbance reading of 0.051. What is the detection
limit?

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