Beruflich Dokumente
Kultur Dokumente
231/2 e
Application Bulletin
Of interest to:
B 1, 2, 9, 16
Sample preparation
Immediately upon taking the water sample, filter it through a microfilter (0.45
m). The filtrates and filters with residues are treated separately. Acidify the filtrates, per litre, with 1 mL conc. HNO3 or HCI. The pH value of the acidified filtrates should lie between 1.7 and 2.0. If this is not the case, more acid must be
added.
Application Bulletin
No. 231/2 e
Page 2
Tap water, surface waters, mineral waters and drinking waters can usually be
analysed without pre-treatment.
Low polluted waste waters can be digested with the 705 UV Digester.
Add 50 - 100 L hydrogen peroxide w(H2O2) = 30% to 10 mL acidified samples
(pH = 2). The quartz tubes are irradiated for 1h at 90C. After cooling to room
temperature, the digested samples can be transferred directly to the polarographic vessel.
The blank value of this digestion is relatively small.
Filters, filter residues and samples with organic matter (foods, pharmaceutics
etc.) must be digested.
- High-pressure asher
- Microwave digestion
Both techniques oxidise the samples in a closed digestion vessel by means of a
mixture of concentrated mineral acids.
- According to Application Bulletin113, open wet digestion with H2SO4 and H2O2
Preparation of sample for the analysis of semiconductor chips:
Place a drop of hydrofluoric acid w(HF) = 40% on chip and fume off by heating.
A white, powdery residue forms. Dissolve this with a drop of nitric acid w(HNO3)
= 65% and rinse into a polarographic vessel. Prepare a blank value with the
same reagents
Remarks
These metals can be determined in the following ranges:
Element
Zn
Cd
Pb
Cu
Tl
Ni
Co
Determination limits
1.0 g/L
0.1 g/L
0.1 g/L
1.0 g/L
0.1 g/L
0.1 g/L
0.1 g/L
Concentration max.
50 mg/L
50 mg/L
50 mg/L
50 mg/L
50 mg/L
10 g/L
10 g/L
Application Bulletin
No. 231/2 e
Page 3
Literature
DIN 38406 Teil 16
Verfahren zur Bestimmung von Zink, Cadmium, Blei, Kupfer, Thallium, Nickel,
Cobalt mittels Voltammetrie. E16 Deutsche Einheitsverfahren.
Ostapczuk, M. Goedde, M. Stppler, H.W. Nrnberg
Kontroll- und Routinebestimmung von Zn, Cd, Pb, Cu, Ni und Co mit differentieller Pulsvoltammetrie in Materialien der deutschen Umweltbank
Fresenius, Z. anal. Chem. 318 (1984) 321-326
Braun, M. Metzger
Umweltanalytische Nickel-Bestimmung durch Adsorptionsvoltammetrie mit der
Quecksilberfilmelektrode
Fresenius, Z. Anal. Chem. 318 (1984) 321-326
G. Van den Berg
Determining trace concentration of copper in water by cathodic film stripping
voltammetry with adsorptive collection
Anal. Lett. 17 A, (1984) 2141-2157 und AB 74
Axel Meyer, Rolf Neeb
Determination of cobalt and nickel by adsorption voltammetry in supporting electrolytes containing triethanolamine and dimethylglyoxime
Fresenius, Z. Anal. Chem. 315 (1983) 118-120
Metrohm Application Bulletin No. 113
Method 1
Determination of Zn, Cd, Pb and Cu
Reagents
All of the used reagents must be of purest quality possible (analytical grade or suprapur). Only ultrapure water should be used.
Sodium hydroxide solution, suprapur, w(NaOH) = 30 %
Acetic acid, suprapur, w(CH3COOH) = 100 %
KCl, suprapur
Zn stock solution, (Zn ) = 1 g/L (commercially available)
2+
Ready-to-use solutions:
KCl-sodium acetate solution: c(KCl) = 1.5 mol/L, c(CH3COONa) = 0.5 mol/L
55.9 g KCl + 25 mL NaOH + 14.2 mL CH3COOH filled up to 500 mL with high
purity water.
Standard solutions:
(Zn ) = 10 mg/L
2+
(Cd ) = 0.1 mg/L
2+
(Pb ) = 0.5 mg/L
2+
(Cu ) = 2.5 mg/L
Diluted solutions are prepared using c(HNO3) = 0.014 mol/L.
2+
Application Bulletin
No. 231/2 e
Page 4
Analysis
Measuring solution:
10 mL (diluted) sample
+ 1 mL KCl-sodium acetate solution
If necessary, adjust the pH of the solution should to 4.6 0.2.
The voltammogram is recorded with the following parameters:
Working electrode
Drop Size
Stirrer/RDE
Measurement mode
Purge time
Pulse amplitude
Deposition potential
Deposition time
Equilibration time
Start potential
End potential
Voltage step
Voltage step time
Sweep rate
Peak potential (Zn)
Peak potential (Cd)
Peak potential (Pb)
Peak potential (Cu)
HMDE
4
2000 rpm
DP
300 s
0.05 V
- 1.15 V
90 s
10 s
- 1.15 V
0.05 V
0.006 V
0.1 s
0.06 V/s
- 0.98 V
- 0.56 V
- 0.38 V
- 0.10 V
Remarks
Ammonium acetate buffer pH 4.6 can be used instead of KCl-sodium acetate
solution. If the sample contains no chloride, it is preferable to use this buffer instead of the KCI/Na acetate solution. Cu achieves peaks with more positive potential (Peak potential Cu: +0.05 V), which are easier to evaluate.
NH4 acetate buffer pH 4.6: c(CH3COOH) = 2 mol/L, c(NH3) = 1 mol/L
55.5 mL w(CH3COOH) = 100 % + 37 mL w(NH3) = 25 % filled up to 500 mL.
Zn is often present in tap water in higher concentrations as the other metals. In
this case, Zn should be determined separately with shorter enrichment time or
after being diluted to a greater extent.
Seeing that the difference of the half wave potentials of TI and Pb is only
approx. 50 mV, TI and Pb are determined together in acetate solutions. For this
reason, following the analysis of Zn, Cd, Pb and Cu, the TI content is then determined according to method 2. If the concentration of Tl is less than 50% of
the concentration of Pb the error for the Pb determination is less than 10%.
If the Tl concentration is more than 50% of the Pb concentration it is not recommended to use method 1 for determination of Pb.
An alternative is a post-electrolysis where a large quantity of the Tl deposited on
the electrode is removed before the determination of Pb.
Application Bulletin
No. 231/2 e
Page 5
-0.43 V
-0.61 V
-0.68 V
Figures
Determination of Zinc, Cadmium, Lead, and Copper acc. to DIN38406/16
tap water
3.00u
Zn
Cu
150n
2.50u
100n
i (A)
i (A)
2.00u
1.50u
Pb
5 0 .0 n
Cd
1.00u
0
- 0 .6 0
- 0 .4 0
E (V )
-0 .2 0
500n
Cd
Pb
-0.60
-0.40
0 .0 0
Cu
0
-1.00
-0.80
-0.20
0.00
E (V)
Zn
c =
+/-
Cd
c = n/a
0.258 mg/l
0.015 mg/l (6.01%)
8.00n
2.50u
2.00u
7.00n
i (A)
i (A)
1.50u
6.00n
1.00u
-0.00023
5.00n
500n
0
-200u
-100u
c / (g/l)
100u
200u
4.00n
800n
1.00u
1.20u
1.40u 1.60u
c / (g/l)
1.80u
Application Bulletin
No. 231/2 e
Page 6
Pb
c =
+/-
Cu
c =
+/-
6.844 g/l
0.398 g/l (5.82%)
6.979 g/l
0.223 g/l (3.19%)
125n
30.0n
100n
75.0n
i (A)
i (A)
20.0n
50.0n
10.0n
25.0n
-6.3e-006
-6.2e-006
0
-5.00u
5.00u
-10.0u
10.0u
c / (g/l)
c / (g/l)
V
uA
----- ------0.989 1.501
-0.989 1.466
-0.989 2.024
-0.989 2.061
-0.989 2.589
-0.989 2.663
Substance : Cd
Mass conc.: n/a
MC.dev.
: n/a
Add.mass :
10.000
VR
---1-1
1-2
2-1
2-2
3-1
3-2
VR
---1-1
1-2
2-1
2-2
3-1
3-2
Comments
------------------
2.042
0.026
0.559
Ovl. in scan
2.626
0.052
0.583
Ovl. in scan
Ovl. in scan
ng
nA
---------4.168
4.215
7.877
8.211
ug/l
ug/l
ng
ng
V
nA
----- ------0.400 15.51
-0.400 15.03
-0.400 26.56
-0.400 27.13
-0.400 35.81
-0.400 37.23
Substance : Cu
Mass conc.:
6.345
Std.Dev. i.delta
------- ------0.024
Comments
------------------
V
---------0.596
-0.596
-0.596
-0.596
Substance : Pb
Mass conc.:
6.222
MC.dev.
:
0.362
Mass
:
68.441
Add.mass :
50.000
i.mean
-----1.483
ug/l
i.mean
--------
Std.Dev. i.delta
------- ---------
4.191
0.050
8.044
0.237
3.853
Comments
-----------------No peak found
No peak found
Ovl. in scan
Ovl. in scan
Ovl. in scan
Comments
------------------
5.82%)
i.mean
-----15.27
Std.Dev. i.delta
------- ------0.339
Comments
------------------
26.84
0.403
11.57
Ovl. in scan
36.52
1.008
9.68
Ovl. in scan
Ovl. in scan
Comments
------------------
Application Bulletin
No. 231/2 e
Page 7
MC.dev.
Mass
Add.mass
:
:
:
0.203
69.791
250.000
VR
---1-1
1-2
2-1
2-2
3-1
3-2
Substance
--------Zn
Cd
Pb
Cu
ug/l
ng
ng
V
nA
----- ------0.132
16.8
-0.132
16.3
-0.120
76.4
-0.120
77.3
-0.114 126.5
-0.114 129.6
Calibr.
-------std.add.
std.add.
std.add.
std.add.
3.19%)
i.mean
-----16.5
Std.Dev. i.delta
------- ------0.349
Comments
------------------
76.8
0.684
60.3
Ovl. in scan
128.1
2.260
51.2
Ovl. in scan
Ovl. in scan
Y.reg/offset
-----------1.480e-006
2.687e-010
1.538e-008
1.665e-008
Final results
--------------------------------Zn =
0.258 mg/l
Cd =
n/a g/l
Pb =
6.844 g/l
Cu =
6.979 g/l
Slope
---------6.328e-003
4.354e-003
2.477e-003
2.626e-003
Nonlin.
----------
Mean deviat.
-----------2.309e-008
2.612e-010
3.278e-010
3.462e-010
Comments
------------------
5.822
3.193
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
Instructions
t/s
------------- ----SMPL>M
DOS>M
PURGE
STIR
300.0
(ADD
PURGE
STIR
10.0
0PURGE
(REP
SEGMENT
REP)1
PURGE
ADD>M
ADD)2
END
Main parameters
------------------------V.fraction
mL
Soln.name
buffer
Rot.speed
2000 /min
Rot.speed
2000 /min
Segm.name
ZnCdPbCu
Soln.name
ZnCdPbCu
Auxiliary parameters
------------------------V.total
L
V.add
1.000 mL
V.add
0.100 mL
Method: AB231_1
SEGMENT
ZnCdPbCu
--------------------------------------------------------------------------------
1
2
3
Instructions
t/s
------------- ----STIR
5.0
HMDE
DPMODE
4
5
6
MEAS
0STIR
SWEEP
7
8
0MEAS
END
90.0
10.0
20.3
Main parameters
------------------------Rot.speed
2000 /min
Drop size
4
U.ampl
50 mV
t.step
0.10 s
U.meas
-1150 mV
Auxiliary parameters
-------------------------
U.start
U.end
U.standby
U.step
Sweep rate
-1150 mV
50 mV
mV
Meas.cell
t.meas
t.pulse
normal
20.0 ms
40.0 ms
6 mV
60 mV/s
Fig. 2 Parameters for the determination of Zn, Cd, Pb, Cu according to method 1
with the 746 VA Trace Analyzer
Application Bulletin
No. 231/2 e
Page 8
Method 2
Determination of Tl
Reagents
All of the used reagents must be of purest quality possible (analytical grade or suprapur). Only ultrapure water should be used.
Sodium hydroxide solution, suprapur, w(NaOH) = 30 %
Acetic acid, suprapur, w(CH3COOH) = 100 %
KCl, suprapur
Ethylenediaminetetraacetic acid disodium salt dihydrate, puriss.p.a., CAS 638192-6
Tl stock solution, (Tl ) = 1 g/L (commercially available)
+
Ready-to-use solutions:
KCl-sodium acetate solution: c(KCl) = 1.5 mol/L, c(CH3COONa) = 0.5 mol/L
55.9 g KCl + 25 mL NaOH + 14.2 mL CH3COOH filled up to 500 mL with high
purity water.
EDTA solution: c(EDTA) = 0.1 mol/L:
Dissolve 0.93 g Na2-EDTA2H2O in H2O and fill up to 25 mL.
Standard solution:
(Tl ) = 0.5 mg/L
Diluted solutions are prepared using c(HNO3) = 0.014 mol/L.
+
Analysis
Measuring solution:
10 mL (diluted) sample
+ 1 mL KCl-sodium acetate solution
(or measuring solution from method 1)
+ 200 L EDTA solution
If necessary, adjust the pH of the solution should to 4.6 0.2.
The voltammogram is recorded with the following parameters:
Working electrode
Stirrer/RDE
Drop size
Measurement mode
Purge time
Pulse amplitude
Deposition potential
Deposition time
Equilibration time
Start potential
End potential
Voltage step
Voltage step time
Sweep rate
Peak potential (Tl)
HMDE
2000 rpm
4
DP
300 s
0.05 V
- 0.8 V
180 s
10 s
- 0.8 V
- 0.2 V
0.006 V
0.1 s
0.06 V/s
- 0.45 V
Application Bulletin
No. 231/2 e
Page 9
Figures
Determination of Thallium acc. to DIN38406/16
tap water_Tl
Tl
c =
+/-
0.319 g/l
0.036 g/l (11.28%)
Tl
6.00n
3.00n
4.00n
2.00n
i (A)
i (A)
5.00n
3.00n
1.00n
2.00n
-2.9e-007
0
-0.70
-0.60
-0.50
-0.40
-500n
-0.30
500n
E (V)
1.00u
1.50u
2.00u
c / (g/l)
V
nA
----- ------0.467 0.549
-0.461 0.511
-0.461 2.063
-0.461 2.165
-0.455 3.812
-0.461 3.764
Calibr.
-------std.add.
i.mean
-----0.530
Std.Dev. i.delta
------- ------0.050
2.114
0.073
1.584
3.788
0.050
1.674
Y.reg/offset
-----------5.207e-010
Final results
--------------------------------Tl =
0.319 g/l
Slope
---------1.815e-003
Comments
------------------
Nonlin.
----------
Mean deviat.
-----------4.755e-011
Comments
------------------
Application Bulletin
No. 231/2 e
Page 10
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Instructions
t/s
------------- ----SMPL>M
DOS>M
DOS>M
PURGE
STIR
300.0
(ADD
PURGE
STIR
10.0
0PURGE
(REP
SEGMENT
REP)1
PURGE
ADD>M
ADD)2
END
Main parameters
------------------------V.fraction
mL
Soln.name
buffer
Soln.name
EDTA_sol
Rot.speed
2000 /min
Rot.speed
2000 /min
Segm.name
Tl_Seg
Soln.name
Tl_Std
Auxiliary parameters
------------------------V.total
L
V.add
1.000 mL
V.add
0.200 mL
V.add
0.020 mL
Method: AB231_2
SEGMENT
Tl_Seg
--------------------------------------------------------------------------------
1
2
3
Instructions
t/s
------------- ----STIR
5.0
HMDE
DPMODE
4
5
6
MEAS
0STIR
SWEEP
7
8
0MEAS
END
180.0
10.0
10.3
Main parameters
------------------------Rot.speed
2000 /min
Drop size
4
U.ampl
50 mV
t.step
0.10 s
U.meas
-800 mV
Auxiliary parameters
-------------------------
U.start
U.end
U.standby
U.step
Sweep rate
-800 mV
-200 mV
mV
Meas.cell
t.meas
t.pulse
normal
20.0 ms
40.0 ms
6 mV
60 mV/s
Method 3
Determination of Ni and Co
Reagents
All of the used reagents must be of purest quality possible (analytical grade or suprapur). Only ultrapure water should be used.
Ammonia solution, suprapur, w(NH3) = 25%
Hydrochloric acid, suprapur, w(HCl) = 30%
Dimethylglyoxim disodium salt octahydrate, puriss.p.a., CAS 75006-64-3
Ni stock solution, (Ni ) = 1 g/L (commercially available)
2+
Ready-to-use solutions:
NH4Cl buffer pH 9.5: c(NH4Cl) = 1 mol/L, c(NH3) = 2 mol/L
112.5 mL NH3 + 53 mL HCl, filled up to 500 mL with high purity water.
DMG solution: c(Na2DMG) = 0.1 mol/L
Dissolve 0.304 g Dimethylglyoxim disodium salt in 10 mL ultrapure water.
Standard solutions:
(Ni ) = 1 mg/L
2+
(Co ) = 0.1 mg/L
Diluted solutions are prepared using c(HNO3) = 0.014 mol/L.
2+
Application Bulletin
No. 231/2 e
Page 11
Analysis
Measuring solution:
10 mL (diluted) sample
+ 0.5 mL NH4Cl buffer
+ 0.1 mL DMG solution
If necessary, adjust the pH of the solution should to 9.5 0.2.
The voltammogram is recorded with the following parameters:
Working electrode
Drop size
Stirrer/RDE
Measurement mode
Purge time
Pulse amplitude
Deposition potential
Deposition time
Equilibration time
Start potential
End potential
Voltage step
Voltage step time
Sweep rate
Peak potential (Ni)
Peak potential (Co)
HMDE
4
2000 rpm
DP
300 s
0.05 V
- 0.7 V
90 s
10 s
- 0.8 V
- 1.25 V
0.004 V
0.3 s
0.013 V/s
- 0.97 V
- 1.13 V
Remarks
If the disodium salt of the dimethylglyoxime should not be used, DMG can be
dissolved in ethanol or triethanolamine.
DMG in ethanol: c(DMG) = 0.1 mol/L
Dissolve 0.29 g DMG in ethanol and fill up to 25 mL.
or
DMG in triethanolamine: c(DMG) = saturated
Dissolve 500 mg dimethylglyoxime in 100 mL TEA:H2O (1:1). This solution is
used when a big excess of Zn disturbs the Co determination.
Na2-Iminodiacetate 0.2 mol/L:
This solution is used in the DIN norm to mask Zn by the Co determination. Our
tests have shown that the determination of Ni besides Co is then not possible
any more because Ni is also complexed.
Application Bulletin
No. 231/2 e
Page 12
Figures
Ni + Co in Meerwasser
Meerwasser
-150n
Ni
-125n
i (A)
-100n
-75.0n
-50.0n
Co
-25.0n
0
-0.80
-0.90
-1.00
-1.10
-1.20
E (V)
Ni
c =
+/-
Co
c =
+/-
0.616 ug/l
0.046 ug/l (7.39%)
2.820 ng/l
0.529 ng/l (18.77%)
-25.0n
-125n
-20.0n
-100n
-15.0n
i (A)
i (A)
-75.0n
-10.0n
-50.0n
-5.00n
-25.0n
-2.6e-009
-5.6e-007
0
-500n
500n
1.00u
1.50u
2.00u
50.0n
c / (g/l)
100n
150n
c / (g/l)
nA
---1-1
1-2
2-1
2-2
3-1
3-2
Substance : Co
------------------
Comments
Application Bulletin
No. 231/2 e
Page 13
Mass conc.:
2.552 ng/l
MC.dev.
:
0.479 ng/l
(
18.77%)
Mass
:
28.201 pg
Add.mass :
1.000 ng
VR
V
nA
i.mean Std.Dev. i.delta
Comments
---- ----- ------ ------ ------- ------1-1
-1.089 -0.32 -0.34
0.050
1-2
-1.086 -0.37
2-1
-1.086 -11.62 -12.26 0.900
-11.91
2-2
-1.086 -12.89
3-1
-1.082 -24.10 -25.02 1.290
-12.76
3-2
-1.082 -25.93
Substance
--------Ni
Co
Calibr.
-------std.add.
std.add.
Y.reg/offset
------------3.049e-008
-3.429e-010
Final results
--------------------------------Ni =
0.616 ug/l
Co =
2.820 ng/l
Slope
----------5.482e-002
-1.354e-001
------------------
------------------
Nonlin.
----------
Mean deviat.
-----------1.254e-009
4.999e-011
Comments
------------------
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16
Instructions
t/s
------------- ----SMPL>M
DOS>M
DOS>M
PURGE
STIR
300.0
(ADD
PURGE
STIR
10.0
0PURGE
(REP
SEGMENT
REP)1
PURGE
ADD>M
ADD)2
END
Main parameters
------------------------V.fraction
mL
Soln.name
buffer
Soln.name
DMG_sol
Rot.speed
2000 /min
Rot.speed
2000 /min
Segm.name
NiCo_Seg
Soln.name
NiCo_Std
Auxiliary parameters
------------------------V.total
L
V.add
0.500 mL
V.add
0.100 mL
V.add
0.010 mL
Method: AB231_3
SEGMENT
NiCo_Seg
--------------------------------------------------------------------------------
1
2
3
Instructions
t/s
------------- ----STIR
5.0
HMDE
DPMODE
4
5
6
MEAS
0STIR
FSWEEP
7
8
0MEAS
END
90.0
10.0
45.9
Main parameters
------------------------Rot.speed
2000 /min
Drop size
4
U.ampl
-50 mV
t.step
0.30 s
U.meas
-700 mV
Auxiliary parameters
-------------------------
U.start
U.end
U.standby
U.step
Sweep rate
-700 mV
-1300 mV
mV
Meas.cell
t.meas
t.pulse
normal
20.0 ms
40.0 ms
4 mV
13.33 mV/s