Dependence of IP on Scan Rate Potential [Se(Iv)] = 2Ppb, 0.1M Hcl Base, E Dep = -0.3V, T Dep = 90S [Se-Cyst] = 25Ppb, 0.1M Hcl Base, E Dep = -0.2V, T Dep = 90S


If the time is too long, the metal ions will diffuse into the mercury drop, affecting the peak height (I p ). Therefore, the electrolysis time for both substances can be chosen in the range of 90s ÷ 150s with the concentration of Se(IV) being 2ppb and Se-Cyst being 25ppb. In fact, we use the electrolysis time for later measurements for both substances as 90s .

c. Study the effect of scanning speed

In polarographic analysis, especially the dissolution voltammetry method, the potential scanning speed has a great influence on the dissolution current intensity. If the potential scanning speed is fast, the analysis time is shortened, the polarographic curve is smooth, but the solubility of the metal in the amalgam with mercury is not good, so the repeatability of the measurement will decrease, that is, the standard deviation of the measurement increases, and the symmetry of the peak also decreases. On the contrary, when the potential scanning speed is slow, the repeatability of the measurement is high, the obtained peak has a balanced shape, especially the separate peaks can be separated for elements with peaks close together on the polarographic line, but the obtained polarographic line is not smooth. Therefore, we must choose a reasonable potential scanning speed to reduce the measurement time while ensuring the accuracy of the measurement and the smoothness of the polarographic curve.

We conducted a study on the potential scanning rate in the range (0.01÷0.06)V/s.

60


50


40


30


20


10


0

0

0.01 0.02 0.03 0.04 0.05 0.06 0.07

Scanning speed (V/s)

Se(IV)

Se-cyst

I (nA)

The research results are presented in Table 3.6 and Figure 3.7.


Figure 3.7: Dependence of I p on the potential scan rate [Se(IV)] = 2ppb, 0.1M HCl background, E dep = -0.3V, t dep = 90s [Se-Cyst] = 25ppb, 0.1M HCl background, E dep = -0.2V, t dep = 90s


Table 3.6: Results of the study of scanning speed measurement


Status

1

2

3

4

5

6

Scanning speed (V/s)

0.01

0.015

0.02

0.03

0.04

0.06


I p (nA)

Se(IV)

10.9

12.4

13.1

13.5

13.5

13.8

Se-Cyst

30.6

37.6

38.8

43.2

43.3

48.8

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The research results show that, when the scanning speed increases, the peak current intensity also increases. However, at fast scanning speed, the baseline is raised, the peak is distorted and unbalanced. From the research results, we decided to choose the scanning speed for future measurements for both substances as 0.02 V/s .

d. Pulse amplitude study

Proceed to record the DPCSV curves of Se(IV) and Se-Cyst when changing the pulse amplitude from 0.02V ÷ 0.15V for Se(IV) and 0.02V ÷ 0.18V for Se-Cyst. The recording results are shown in Table 3.7 and Figure 3.8.

Se(IV) Se-Cyst

0.05 V

0.05V


Figure 3.8: DPCSV curve of Se(IV) and Se-Cyst studying pulse amplitude

[Se(IV)] = 2ppb, 0.1M HCl background, E dep = -0.3V, t dep = 90s, scan rate 0.02V/s [Se-Cyst] = 25ppb, 0.1M HCl background, E dep = -0.2V, t dep = 90s, scan rate 0.02V/s


Table 3.7: Pulse amplitude measurement results


Status

1

2

3

4

5

6

Pulse Amplitude (V)

0.03

0.05

0.08

0.12

0.15

0.18


I p (nA)

Se(IV)

9.3

13.9

17.9

16.9

Variable

form


Se-Cyst

18.9

31.1

33.8

39.3

47.3

Are not

balance


The research results show that I p increases when the pulse amplitude increases, however, when the pulse amplitude increases (from 0.15 for Se(IV) and 0.18 for Se-Cyst and above), the peak is distorted and unbalanced. From that result, we choose the optimal pulse amplitude for the analysis of Se(IV) and Se-Cyst as 0.05V .

e. Pulse timing study

We conducted a study on pulse placement time in the range of 0.005s÷0.06s and obtained the results in table 3.8 and figure 3.9.

Se(IV) Se-Cyst

1

2

3 (0.02s)

1

2

3 (0.02s)

Figure 3.9: DPCSV curves of Se(IV) and Se-Cyst studying pulse setting time

[Se(IV)] = 2ppb, 0.1M HCl background, E dep = -0.3V, t dep = 90s, scan rate 0.02V/s, pulse amplitude 0.05V

[Se-Cyst] = 25ppb, 0.1M HCl background, E dep = -0.2V, t dep = 90s, scan rate 0.02V/s, pulse amplitude 0.05V


Table 3.8: Measurement results of research to select optimal pulse placement time


Status

1

2

3

4

5

t(s)

0.005

0.010

0.020

0.040

0.060


I p (nA)

Se(IV)

47.9

25.0

16.6

10.2

7.2

Se-Cyst

160.0

102.0

74.5

37.0

25.0


Comment:

When the pulse setting time is small, I p is high, but the pic pin is high (pic 1, pic 2). If the pulse setting time increases, I p decreases, but the resulting pic is balanced, the pic pin is low (pic 3). If we continue to increase the pulse setting time, I p is low again. From that result, we choose the pulse setting time to be 0.02s (pic 3).

f. Study the speed of stirring the solution

During the electrolysis enrichment process, to help the active substances diffuse evenly to the electrode surface, ensuring that the concentration of the active substance in the solution layer close to the electrode surface remains constant, the solution must be stirred throughout the enrichment period. The solution stirring process is completely automatic using a stirring rod at different speeds for each different analysis solution.

We conducted research on the solution stirring speed in the range of 400÷2800 rpm, obtaining the results in table 3.9 and figure 3.10.

Table 3.9: Measurement results of research to select optimal solution stirring speed


Status

1

2

3

4

5

6

V (rpm)

400

800

1200

2000

2400

2800


I p (nA)

Se(IV)

8.3

11.7

14.5

16.6

17.5

17.7

Se-Cyst

29.5

47.3

49.4

56.5

62.1

65.9


Se(IV) Se-Cyst

2000 rpm

2000 rpm

Figure 3.10: DPCSV curves of Se(IV) and Se-Cyst

study of solution stirring speed

[Se(IV)] = 2ppb, 0.1M HCl background, E dep = -0.3V, t dep = 90s,

scan rate 0.02V/s, pulse amplitude 0.05V, pulse time 0.02s [Se-Cyst] = 25ppb, HCl background 0.1M, E dep = -0.2V, t dep = 90s,

scan rate 0.02V/s, pulse amplitude 0.05V, pulse time 0.02s

The research results show that: the higher the speed of stirring the solution, the higher the I p but the peak leg also rises. We also studied the repeatability of the measurement at different stirring speeds, the results showed that the speed of 2000 rpm gave the best repeatability. On the other hand, at too high a stirring speed, it will create eddies in the solution, affecting the measurement results and possibly causing the mercury drops to fall. Therefore, to ensure the stability and accuracy of the measurement, the obtained peak is balanced, we chose the stirring speed of 2000 rpm .

g. Study of mercury droplet size

In the HMDE electrode dissolution voltammetry method, the repeatability of the mercury droplet size directly affects the repeatability of the measurement. Changing the size of the mercury droplet changes the surface area of ​​the droplet, which in turn changes the amount of precipitate deposited on the droplet surface. Therefore, we conducted a study on the dependence of the peak height (I p ) on the size of the mercury droplet, the results are shown in Table 3.10 and Figure 3.11.


Table 3.10: Measurement results of research to select optimal mercury droplet size


Status

1

2

3

4

5

6

7

8

9

Droplet size

1

2

3

4

5

6

7

8

9

I p (nA)

Se(IV)

7.2

10.8

12.8

14.9

15.7

16.8

17.9

18.5

18.9

Se-Cyst

30.8

41.8

50.9

61.3

73.2

79.3

88.9

95.2

102.0


Figure 3.11: Dependence of I p on mercury droplet size [Se(IV)] = 2ppb, HCl background 0.1M, E dep = -0.3V, t dep = 90s, scan rate 0.02V/s, pulse amplitude 0.05V, pulse setting time 0.02s, stirring speed 2000r/min

[Se-Cyst] = 25ppb, HCl background 0.1M, E dep = -0.2V, t dep = 90s, pulse amplitude 0.05V, pulse time 0.02s, scan rate 0.02V/s, stirring speed 2000rpm

Comment:

When the size of the mercury droplet increases, I p increases. However, when the droplet size is large, the peak foot is raised. On the other hand, large droplet size also makes it easy for the droplet to fall during the measurement. Therefore, we choose the droplet size of 6 in the following measurements.

h. Study of equilibrium time (rest time)

The equilibrium time is the transition time from the electrolysis recording stage to the dissolution recording stage (reverse potential scanning). During this recording stage, the solution is stopped stirring and left to stand still for a while so that the precipitated metal is evenly distributed on the surface of the mercury drop, thus the polarographic curve will be smooth, the sensitivity and accuracy of the measurement will increase. Therefore, we conducted a study on the dependence of peak height (I p ) on the equilibrium time. The research results are presented in Table 3.11 and Figure 3.12.


Table 3.11: Measurement results of the study to select the optimal equilibrium time


Status

1

2

3

4

5

6

rest time (s)

5

10

15

20

30

40

I p (nA)

Se(IV)

15.8

16.0

16.2

16.4

17.2

16.9

Se-Cyst

72.6

72.3

74.6

74.8

77.2

79.3


Figure 3.12: Dependence of I p on equilibrium time

[Se(IV)] = 2ppb, 0.1M HCl background, E dep = -0.3V, t dep = 90s, scan rate 0.02V/s pulse amplitude 0.05V, pulse setting time 0.02s, stirring speed 2000r/min

[Se-Cyst] = 25ppb, HCl background 0.1M, E dep = -0.2V, t dep = 90s, scan rate 0.02V/s, pulse amplitude 0.05V, pulse setting time 0.02s, stirring speed 2000r/min

Comment:

We can see that when the equilibrium time reaches 10 seconds (for Se(IV)) and 15 seconds (for Se-Cyst), I p reaches a stable value. However, during the research process, we conducted many times to evaluate the repeatability of the measurement results; the results showed that the equilibrium time of 15 seconds gave the best repeatability. When the equilibrium time was longer, the repeatability of the measurement results decreased, which is explained by the fact that when the equilibrium time was too long, the amount of precipitate absorbed into the mercury droplet affected the repeatability of the measurement. Therefore, we chose the equilibrium time of 15 seconds for the following experiments.

i. Study on oxygen removal time (N2 aeration time )

At room temperature and atmospheric pressure, the concentration of dissolved O 2 in the analytical solution is usually about 2.10 -3 M. On the mercury electrode, dissolved oxygen gives 2 waves:


- The wave corresponding to the process of reducing O 2 to H 2 O 2 , occupies the potential range of 0 0.9 V when

The reference electrode is the calomel electrode.

- The wave corresponding to the reduction process of H 2 O 2 to H 2 O (in acidic environment) or reduction to OH - (in alkaline or neutral environment), occupies the potential range -0.9 1.2 V.

Thus, when studying the cathode potential region (0  -1.5)V, those O 2 waves affect the dissolved Vol-Ampere signal of the analytes, hindering the measurement. Therefore, it is necessary to have measures to remove oxygen from the analytical solution by bubbling inert gas (N 2 or Ar) or using chemical agents (Na 2 SO 3 in alkaline environment or ascorbic acid in acidic environment ...).

We used nitrogen gas to expel oxygen from the analysis solution. The results of the study on the effect of aeration time on the current intensity I p are obtained in the table.

3.12 and figure 3.13.

Se(IV) Se-Cyst

300s

0s

300s

Figure 3.13: DPCSV curve of Se(IV) and Se-Cyst studying oxygen removal time

[Se(IV)] = 2ppb, 0.1M HCl background, E dep = -0.3V, t dep = 90s, scan rate 0.02V/s pulse amplitude 0.05V, pulse setting time 0.02s, stirring speed 2000rpm, rest time = 15s [Se-Cyst] = 25ppb, 0.1M HCl background, E dep = -0.2V, t dep = 90s, scan rate 0.02V/s pulse amplitude 0.05V, pulse setting time 0.02s, stirring speed 2000rpm, rest time = 15s

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