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Electronics and
electroplating applications
Application brochure 28
Contents
Page 2/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
M189 Determination of free cyanide in a copper bath ......................................................... 56
M190 Determination of free cyanide in a cyanidic zinc bath .............................................. 58
M191 Back-titration of zinc in a cyanidic zinc bath ............................................................ 60
Literature ........................................................................................................................................... 96
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 3/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 5
Mean value x = 1.393 g/L Copper (Cu)
Standard deviation s = 0.0126 g/L Copper (Cu)
Rel. standard deviation srel = 0.902 %
Outlier test: no outliers
Page 4/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 062 Chem. Copper Electrolyte
Version 20-Jun-1991 11:28 Bath composition
Title
Method ID . . . . . . . . . . . . . 062
This bath is used for chemical copper deposition on
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . Chem. Copper Electrolyte
. . . . 20-Jun-1991 11:28
printed circuit boards. It consists of sodium hydrox-
Sample ide, formaldehyde, weakly complexed copper, free
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . Stand 1 complexing agent(s), and additives.
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 10.0
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 0.0 Sample preparation
Equivalent number z . . . . . . . . 1
Stir Be careful! If cyanide is present in the sample, the
Speed [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . . . . . . 10 addition of a sulphuric acid solution must be performed
Titration
Titrant . . . . . . . . . . . . . . Na2S2O3 in a ventilated fume hood (formation of HCN!).
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DM140-SC 1) A weak copper complex is decomposed at room
Unit of meas . . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP temperature by the acid medium. A stronger com-
Predispensing 1 . . . . .
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
mL
1.0
plex is decomposed in the same way at elevated
Titrant addition . . . .
∆V [mL] . . . . . . .
.
.
.
.
.
.
.
.
INC
0.1
temperature.
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 2) After decomposition the sample is cooled at room
∆t [s] . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 temperature.
t(max) [s] . . . . . . . . . . 30.0
Threshold
EQP range
. . . . . . .
. . . . . . .
.
.
.
.
.
.
.
.
100.0
Yes
3) Then potassium iodide (KI) and potassium thiocy-
Limit A [mV, pH,...] . . . . . 800.0 anate (KSCN) are added.
Limit B [mV, pH,...] . . . . . 0.0
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes 4) Cu(II) is reduced with excess iodide (I-) and subse-
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard quently precipitated as CuI in the presence of thio-
Calculation
Result name . . . . . . . . . . . . Copper (Cu)
cyanate (SCN-). KSCN is added to avoid adsorp-
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R1=Q*C1/U
C1=63.546/z
tion of I2 on the surface of CuI :
2 Cu2+ + 4 I - → 2 CuI + I2
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . CuSO4
Formula . . . . . . . . . . . . . . R2=Q*C2/U The amount of iodine formed is proportional to the
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C2=159.60/z
g/L
Cu(II) content. Cover the beakers to avoid loss of
Decimal places . . . . . . .
Calculation
. . . . 3 iodine
Result name . . . . . . . . . . . . CuSO4.5H2O
Formula . . . . . . . . . . . . . . R2=Q*C2/U 5) The complete reduction of Cu(II) requires 5 min.
Constant . . . . . . . . . . . . . . C2=249.68/z
Decimal places . . . . . . . . . . . 3
Record
Output unit . . . . . . . .
Result last sample . . . . .
. . . . Printer
. . . . Yes
Titration of iodine
E - V curve . . . . . . . . . . . . Yes
Statistics I2 is titrated at room temperature with Na2S2O3:
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
.
.
.
.
.
.
.
.
R1
Yes 2 S2O32- + I2 → S4O62- + 2 I-
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
• Stir moderately. Vigorous stirring causes loss of I2
Record
Output unit . . . . . . . . . . . . Printer
• Alternative: Photometric indication with DP550
All results . . . . . . . . . . . . Yes Phototrode; indicator: starch
• Titration time: approx. 4 minutes
Literature
E-V curve
1. B. Bressel, Ausserstromloser Kupferelekrolyt,
DGO Deutsche Gesellschaft für Galvano- und
Oberflächentechnik e.V., Horionplatz 6,
Düsseldorf (Germany), 1988
2. Copper bath's manufacturer
Disposal
Copper solutions: special waste
Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators. Author: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 5/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 5
Mean value x = 20.407 mmol/L Free Compl.
Standard deviation s = 0.0089 mmol/L Free Compl.
Rel. standard deviation srel = 0.044 %
Outlier test : sample No. 1/3
Page 6/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 063
Version
Free Complexing Agents
23-Jul-1991 15:25 Bath composition
Title
Method ID . . . . . . . . . . . . . 063
• This bath is used for chemical copper deposition
Title . . . . . . . . . . . . . Free Complexing Agents on printed circuit boards. It consists of sodium hy-
Date/time . . . . . . . . . . . . . 23-Jul-1991 15:25
Sample droxide, formaldehyde, weakly complexed copper,
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . Stand 1 free complexing agent(s), and additives.
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 10.0 • Depending on the use of the bath a single specific
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
********
0.0
complexing agent or a mixture of various complex-
Equivalent number z . . . .
Stir
. . . . 1 ing agents is used. Results are given in mmol/L.
Speed [%] . . . . . . . . . . . . . 40 • The free complexing agents influence the rate of
Time [s] . . . . . . . . . . . . . . 10
Titration copper deposition and the stability of the bath.
Titrant . . . . . . . . . . . . . . CuSO4-(2)
Concentration [mol/L] . . . . . . . 0.01
Sensor . . . . . . . . . . . . . . DP550
Unit of meas . . . . . . . . . . . . mV Sample preparation
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL 1) The copper bath is diluted and then titrated with
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . INC 0.01 M Cu(II) titrant. No pH buffer is added, the
∆V [mL] . . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . EQU sample is alkaline.
∆E [mV] . . . . . . . . . . . 2.0
∆t [s] . . . . . . . . . . . 2.0 2) It is recommended to use a trituration 1:500 murex-
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 ide: NaCl.
Threshold . . . . . . . . . . . 100.0
EQP range . . . . . . . . . . . Yes
Limit A [mV, pH,...] . . . . . 0.0 3) Add the indicator before starting analysis. Keep
Limit B [mV, pH,...] . . . . . 1000.0
Maximum volume [mL] . . . . . . . 40.0 sample free of air bubbles during titration. Air
Termination after n EQPs
n = . . . . . . . . .
.
.
.
.
.
.
.
.
Yes
1
bubbles and undissolved impurities affect with the
Evaluation procedure . .
Calculation
. . . . Standard photometric indication.
Result name . . . . . . . . . . . . Free compl.
Formula . . . . . . . . . . . . . . R1=Q*C1/U
Constant . . . . . . . . . . . . . . C1=1000
Result unit . . . . . . . . . . . . mmol/L Titration
Decimal places . . . . . . . . . . . 3
Record
Output unit . . . . . . . . . . . . Printer
Free complexing agents are titrated with Cu(II)-solu-
Result last sample . . . . . . . . . Yes tion in alkaline solution:
Cu 2+ + Agent → Cu-Agent 2+
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes At the equivalence point (simplified):
Rel. standard deviation srel
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes Cu 2+ + Murexide - → Cu-Murexid + (violet-yellow)
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes • Adjust the DP 550 at 1000 mV in deionised water
before starting titration (100% transmission).
Literature • Due to the steep signal change, an EQP titration
1. B. Bressel, Ausserstromloser Kupferelekrolyt, with fixed increments is used. The low threshold
DGO Deutsche Gesellschaft für Galvano- und value allows for different amounts of indicator.
Oberflächentechnik e.V., Horionplatz 6, • A fixed predispensing shortens the titration time.
Düsseldorf (Germany), 1988. • Titration time: approx. 4 minutes.
2. Copper bath's manufacturer
E-V curve
Disposal
Copper solutions: special waste
Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators.
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 7/100
METTLER TOLEDO
Standard: Tris(hydroxymethyl)aminomethane
RESULTS
STATISTICS
Number results R1 n = 5
Mean value x = 12.2 pH Dil. sample
STATISTICS
Number results R2 n = 5
Mean value x = 14.56 g/L NaOH
Standard deviation s = 0.047 mmol/L
Rel. standard deviation srel = 0.319 %
Outlier test : no outliers!
STATISTICS
Number results R4 n = 5
Mean value x = 8.58 g/L Formaldehyde
Standard deviation s = 0.109 g/L Formaldehyde
Rel. standard deviation srel = 1.273 %
Outlier test : no outliers!
Page 8/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method
Method 064 Hydroxide and Formaldehyde
Version 18-Jun-1991 11:05 Calculation
Result name . . . . . . . . . . . . Formaldehyde
Title Formula . . . . . . . . . . . . . . R4=Q[2]*C4/U 7
Method ID . . . . . . . . . . . . . 064 Constant . . . . . . . . . . . . . . C4=30.03/1
Title . . . . . . . . . . . . . . . Hydroxide and Result unit . . . . . . . . . . . . g/L
Formaldehyde Decimal places . . . . . . . . . . . 2
Date/time . . . . . . . . . . . . . 18-Jun-1991 11:05 Condition . . . . . . . . . . . . . Yes
Instruction Condition . . . . . . . . . . R2>0
Instruction . . . . . . . . . . . . Analysis to be done Calculation
> . . . . . . . . . . . . . . . . . after correction of Result name . . . . . . . . . . . . Correction
> . . . . . . . . . . . . . . . . . the copper content. Formula . . . . . . . . . . . . . . R5=8.5-(Q[2]*C5/U) 8
Sample Constant . . . . . . . . . . . . . . C5=30.03/1
Number samples . . . . . . . . . . 5 Result unit . . . . . . . . . . . . g/L
Titration stand . . . . . . . . . . Stand 1 Decimal places . . . . . . . . . . . 2
Entry type . . . . . . . . . . . . . Fixed volume U Condition . . . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 5.0 Condition . . . . . . . . . . . R2>0
ID1 . . . . . . . . . . . . . . . . ******** Instruction
Molar mass M . . . . . . . . . . . . 0.0 Instruction . . . . . . . . . . . . Sodium hydroxide
Equivalent number z . . . . . . . . 1 > . . . . . . . . . . . . . . . . . content too high.
Stir > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
Speed [%] . . . . . . . . . . . . . 50 Condition . . . . . . . . . . . . . Yes
Time [s] . . . . . . . . . . . . . . 10 Condition . . . . . . . . . . . R2>16
Measure Instruction
Sensor . . . . . . . . . . . . . . DG111-SC-(2) Instruction . . . . . . . . . . . . Sodium hydroxide
Unit of meas . . . . . . . . . . . . As installed > . . . . . . . . . . . . . . . . . content too low.
∆E [mV] . . . . . . . . . . . . . . 0.5 > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
∆t [s] . . . . . . . . . . . . . . 3.0 Condition . . . . . . . . . . . . . Yes
t(min) mode . . . . . . . . . . . . Fix Condition . . . . . . . . . . . R2<12
t(min) [s] . . . . . . . . . . . 30.0 Instruction
t(max) [s] . . . . . . . . . . . . 300.0 Instruction . . . . . . . . . . . . Formaldehyde content
Calculation > . . . . . . . . . . . . . . . . . too high
Result name . . . . . . . . . . . . Dil. sample > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
Formula . . . . . . . . . . . . . . R1=E Condition . . . . . . . . . . . . . Yes
Constant . . . . . . . . . . . . . . Condition . . . . . . . . . . . R4>10
Result unit . . . . . . . . . . . . pH Instruction
Decimal places . . . . . . . . . . . 1 Instruction . . . . . . . . . . . . Formaldehyde content
1 Titration > . . . . . . . . . . . . . . . . . too low
Titrant . . . . . . . . . . . . . . HCl > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
Concentration [mol/L] . . . . . . . 0.1 Condition . . . . . . . . . . . . . Yes
Sensor . . . . . . . . . . . . . . DG111-SC-(2) Condition . . . . . . . . . . . R4<7
Unit of meas . . . . . . . . . . . . As installed Record
Titration mode . . . . . . . . . . . EP Output unit . . . . . . . . . . . . Printer
Predispensing . . . . . . . . . . mL Result last sample . . . . . . . . . Yes
Volume [mL] . . . . . . . . . 1.0 E - V curve . . . . . . . . . . . . Yes
Titrant addition . . . . . . . . Continuous Statistics
Control band [mV, pH,...]. . . 0.3 Ri (i=index) . . . . . . . . . . . . R1
Delay [s] . . . . . . . . . . 10 Statistics
End point mode . . . . . . . . . EPA Ri (i=index) . . . . . . . . . . . . R2
Potential [mV, pH,...] . . . . 10.5 Standard deviation s . . . . . . . . Yes
Tendency . . . . . . . . . . . . Negative Rel. standard deviation srel . . . . Yes
Maximum volume [mL] . . . . . . . 30.0 Outlier test . . . . . . . . . . . . Yes
2 Calculation Statistics
Result name . . . . . . . . . . . . NaOH Ri (i=index) . . . . . . . . . . . . R4
Formula . . . . . . . . . . . . . . R2=Q1*C2/U Standard deviation s . . . . . . . . Yes
Constant . . . . . . . . . . . . . . C2=40/1 Rel. standard deviation srel . . . . Yes
Result unit . . . . . . . . . . . . g/L Outlier test . . . . . . . . . . . . Yes
Decimal places . . . . . . . . . . . 2 Record
3 Calculation Output unit . . . . . . . .
All results . . . . . . . .
. . . . Printer
. . . . Yes
Result name . . . . . . . . . . . . Correction
Formula . . . . . . . . . . . . . . R3=14-(Q1*C3)/U
Constant . . . . . . . . . . . . . . C3=40/1
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 Remarks
Record
Output unit . . . . . . . . . . . . Printer
Result last sample . . . . . . . . . Yes • The electrode DG111-SC is calibrated in the
4 E - V curve . . . . . . . . . . . . Yes
Dispense range of pH 9 to 12 (see application M004).
Titrant . . . . . . . . . . . . . . Na2SO3 (pH 10.5)
Concentration [mol/L] . . . . . . . 1.0
Volume [mL]. . . . . . . . . . . . . 10.0 • Hydrochloric acid is standardized with THAM
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>0 (see application M003).
5 Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60
• The pH value of the sodium sulphite solution
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>0
(Titrant 2) has to be adjusted to the same end-
6 Titration pont value as in the titration (see 6). Otherwise
Titrant . . . . . . . . . . . . . . HCl
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DG111-SC-(2)
complicated blank evaluations are necessary.
Unit of meas . . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EP • Total analysis time: approx. 4 minutes.
Predispensing . . . . . . . . . . mL
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . Continuous • The titrator displays warnings if upper or lower
Control band [mV, pH,...]. . . 0.2
Delay [s] . . . . . . . . . . 10 result limits are exceeded.
End point mode . . . . . . . . . EPA
Potential [mV, pH,...] . . . . 10.5
Tendency . . . . . . . . . . . . Negative
Maximum volume [mL] . . . . . . . 30.0
Condition . . . . . . . . . . . . Yes
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 9/100
Comments to method 064
1. EPA Titration:
Continuous endpoint titration to pH 10.5, i.e. the pH value of endpoint as indicated in the litera-
ture of the manufacturer. No overtitration. This titration allows the determination of the NaOH-
content.
2. Calculation R2:
NaOH-content in g/L.
3. Calculation R3:
Calculation of the bath correction in g NaOH/L This value is the difference between the nominal
value 14 and the actual result. The nominal value is indicated by the manufacturer.
4. Dispense:
10 mL sodium sulphite solution c(Na2SO3) = 1.0 mol/L are dispensed. The pH value of this
reagent must first be adjusted according to the pH endpoint of the subsequent EPA titration (see
6) , in this case pH 10.5.
5. Stir:
During stirring time the following reaction takes place:
Formaldehyde (HCHO) reacts with sodium sulphite, and sodium hydroxide is formed beside
CH2OH•SO3Na.
6. EPA Titration:
Continuous endpoint titration to pH 10.5, as indicated in the literature of the manufacturer. With
this titration the NaOH formed is titrated, and from the equivalent amount of NaOH the conce-
tration of formaldehyde is determined.
7. Calculation R4:
Calculation of the formaldehyde content in g/L
8. Calculation R5:
Calculation of the bath correction in g formaldehyde/L . This value is the difference between the
nominal value 8.5 and the actual result. The nominal value is indicated by the manufacturer.
Bath composition
• The electroless alkaline copper bath is used for the deposition of relatively thick layers of copper
on printed circuit boards. The procedure is based on the chemical reduction of (weakly) complexed
copper (II) ions at activated catalytic surfaces.
• This type of bath usually contains copper, complexing agent or mixture of complexing agents,
alkali (e.g. NaOH), formaldehyde as a reducing agent, and additives.
• The periodic bath control by titration is necessary for optimal applicaition of the bath., The content
of copper (II) ions (see application M062), of free complexing agents (M063), of hydroxide and
formaldehyde as well as the pH value (this application) are determined. Concentrations values
outside the limits cause failures.
Page 10/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
E-V curve: NaOH content E-V curve: Formaldehyde content
Literature
1. B. Bressel, Ausserstromloser Kupferelekrolyt, DGO Deutsche Gesellschaft für Galvano- und
Oberflächentechnik e.V., Horionplatz 6, Düsseldorf (Germany), 1988
2. Copper bath's manufacturer
Disposal
Copper solutions: special waste
Other titrators
DL77 titrator.
RESULTS
STATISTICS
Number results R1 n = 5
Mean value x = 29.07 g/L NaH2PO2
STATISTICS
Number results R2 n = 5
Mean value x = 35.02 g/L NaH2PO2•H2O
Standard deviation s = 0.150 g/L NaH2PO2•H2O
Rel. standard deviation srel = 0.428 %
Outlier test: no outliers!
STATISTICS
Number results R3 n = 5
Mean value x = -9.02 g/L Correction
Page 12/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 065a / Content determination Remarks
Method 065a Hypophosphite in Chem.Ni
Version 18-Nov-1991 14:51
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 13/100
Results and table of measured values
RESULTS
SAMPLE
No. 1/4
Titration stand Stand 1
Identification Chem.Ni 13.55
Volume U = 3.0 mL
Correction factor f = 1.0
MEASURED VALUES
Titrant Na2S2O3 0.1 mol/L t = 0.99896
Drive Drive 2 20 mL
Sensor DM140-SC
Page 14/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 065b / Iodine solution Remarks
Method 065b Aux. value for M065/M067
Version 19-Nov-1991 14:12
Sample preparation Method 065b
Title
Method ID . . . . . . . . .
Title . . . . . . . . .
. . . . 065b
. . . . Aux. value for M065/M067
1) 50 mL sulphuric acid solution 20% are given
Date/time . . . . . . . . .
Sample
. . . . 19-Nov-1991 14:12 into a titration beaker.
Number samples . . . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1 2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 0.0 dispensed automatically by the titrator using
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 0.0 the function "Dispense" in method 065b.
Equivalent number z . . . . . . . . 1
Stir
Speed [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . .
Dispense
. . . . 5
Titration
Titrant . . . . . . . . . . . . . . 1/2 I2
Concentration [mol/L] . . . . . . . 0.1
Volume [mL] . . . . . . . . . . . . 20.0 1) Iodine is titrated with sodium thiosulphate:
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 40
. . . . 20
I2 + 2 S2O32- → 2 I- + S4O62-
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
Na2S2O3
0.1
2) Sodium thiosulphate is standardized with po-
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
.
.
.
.
.
.
.
.
DM140-SC
mV
tassium iodate (see application M009).
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL 3) The mean value of a series of three sample is
Volume [mL] . . . . . . . . . 15.0
Titrant addition . . . . . . . . DYN automatically stored as auxiliary value H3 and
∆E(set)[mV] . . . . . . . . . 4.0
Limits ∆V . . . . . . . . . . Relative can therefore by applied by method 065a for
∆V(min) [%dosVol] . . . . . 0.1
∆V(max) [%buVol]. . . . . . 1.5 the determination of nickel.
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 3.0 4) The storage of the mean value only occurs if it
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 is comprised between the limits 1.5 and 2.5
Threshold . . . . . . . . . . . 150.0
EQP range . . . . . . . . . . . Yes mmol which assure an adequate cocnentration.
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . -1000.0
Maximum volume [mL] . . . . . . . 30.0 5) The shelf life of the iodine solution is limited.
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 We recommend to perfom method 065b before
Evaluation procedure . . . . . . Standard
Calculation each nickel content determination.
Result name . . . . . . . . . . . . Consumption
Formula . . . . . . . . . . . . . . R1=Q1
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mmol
Decimal places . . . . . . . . . . . 4
Record
Output unit . . . . . . . . . . . . Printer
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Auxiliary value
ID text . . . . . . . . . . . . . . Aux.M065/M067
Formula . . . . . . . . . . . . . . H3=x[1]
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . 1.5<x<2.5
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Disposal
Nickel solutions: special waste
Other titrator
DL77 titrator.
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 15/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 6
Mean value x = 5.74 g/L Ni Content
Standard deviation s = 0.012 g/L Ni Content
Rel. standard deviation srel = 0.211 %
Outlier test: no outliers!
Page 16/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 066 Remarks
Method 066 Ni in Chem. Ni-Electrolyte
Version 13-Sep-1991 13:39 • The buffer pH 10 is prepared by addition of
Title 570 mL conc. NH3 and 70 g NH4Cl in a 1 L flask.
Method ID . . . . . . . . . . . . . 066
Title . . . . . . . . . . . . . Ni in Chem. Ni-Electrolyte
Deionised water is added to 1 L.
Date/time . . . . . . . . . . . . . 13-Sep-1991 13:39
Instruktion • The shape of the titration curve is somewhat af-
Instruction . . . . . . . . . . . . 10mL NH3-Buffer, pH 10
> . . . . . . . . . . . . . . . . . + ca. 200 mg 1 : 500 fected by the concentration of the indicator. The
> . . . . . . . . . . . . .
Sample
. . . . Murexide trituration
results, however, do not differ significantly (tested
Number samples . . . . . .
Titration stand . . . . . .
.
.
.
.
.
.
.
.
6
Stand 1
range: 25-500 mg 1:500 murexide : NaCl tritura-
Entry type . . . . . . . . . . . . . Fixed volume U tion pe sample).
Volume [mL] . . . . . . . . . . . 5.0
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 58.69 • The results are given in g/L using the molar mass
Equivalent number z . . . . . . . . 1
Stir
M.
Speed [%] . . . . . . . . . . . . . 60
Time [s] . . . . . . . . . . . . . . 10 M(Ni) = 58.69 g/mol
Titration
Titrant . . . . . . . . . . . . . . EDTA
Concentration [mol/L] . . . . . . . 0.1 M(NiCl2) = 129.6 g/mol
Sensor . . . . . . . . . . . . . . DP550
Unit of meas . . . . . . . .
Titration mode . . . . . . .
.
.
.
.
.
.
.
.
As installed
EQP
M(NiCl2•6H2O) = 237.7 g/mol.
Predispensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 1.0 • Nickel ions forms a yellow complex with murex-
Titrant addition . . . . . . . . DYN
∆E(set)[mV] . . . . . . . . . 8.0 ide in alkaline solution:
Limits ∆V . . . . . . . . . . Absolute
∆V(min) . . . . . .
∆V(max) . . . . . .
.
.
.
.
.
.
.
.
0.05
0.2
Ni 2+ + Murexide - = Ni-Murexid+
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 2.0 By adding EDTA, Ni forms a more stable complex
∆t [s] . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 2.0 with EDTA:
t(max) [s] . . . . . . . . . . 15.0
Threshold
EQP range
. . . . . . .
. . . . . . .
.
.
.
.
.
.
.
.
10.0
Yes
Ni-Murexid+ + EDTA 4- = Ni-EDTA2-+ Murexide-
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . 0.0 At the equivalence point, all Ni ions have been
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes complexed by EDTA and murexide is free in the
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard alkaline solution. There is a colour change from
Calculation
Result name . . . . . . . . . . . . Ni Content
yellow to blue-violet.
Formula . . . . . . . . . . . . . . R1=Q*C1/U
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C1=M/z
g/L
• Nickel content of different baths:
Decimal places . . . . . . . . . . . 2
Record Bath n Content / g/L srel / %
Output unit . . . . . . . . . . . . Printer
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics LR-6/A 5 5.65 0.254
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
.
.
.
.
.
.
.
.
R1
Yes
LR-37K 6 5.67 0.253
Rel. standard deviation srel . . . . Yes LR-200 6 5.74 0.211
Outlier test . . . . . . . . . . . . Yes
Record ALT/IC 5 5.38 0.128
Output unit . . . . . . . .
All results . . . . . . . .
. . . . Printer
. . . . Yes
NM/a-1 6 5.36 0.206
IG/3-6 6 6.41 0.219
Disposal
Nickel solutions: special waste
Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77.
Author: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 17/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 8
Mean value x = 189.86 g/L Na2HPO3
Standard deviation s = 0.196 g/L Na2HPO3
Rel. standard deviation srel = 0.103 %
Outlier test: no outliers!
STATISTICS
Number results R2 n = 8
Mean value x = 156.72 g/L NaH2PO3
STATISTICS
Number results R3 n = 8
Mean value x = 123.59 g/L NaH2PO3
Page 18/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 067 Remarks
Method 067 Orthophosphite in Chem.Ni
Version 21-Nov-1991 12:44 Electroless nickel bath
Title
Method ID . . . . . . . . . . . . . 067 • Orthophosphite affects the behaviour of the bath.
Title . . . . . . . . . . . . . Orthophosphite in Chem.Ni
Date/time . . . . . . . . . . . . . 21-Nov-1991 12:44
The bath must be replaced as soon as a specific
Sample
Number samples . . . . . . . . . . 8
concentration is reached.
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.5
********
Sample preparation (Method 067)
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z . . . . . . . . 2 1) Add 20 mL 5% NaHCO3 to the sample.
Dispense
Titrant . . . . . . . . . . . . . . Acetic acid
Concentration [mol/L] . . . . . . . 2 2) 20 mL iodine c(1/2 I2) = 0.1 mol/L are dispensed
Volume [mL] . . . . . . . . . . . . 20.0
Stir using the auxiliary function "Dosing" of the titra-
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 40
. . . . 20
tor. Cover the beaker to prevent loss of iodine.
Titration
Titrant . . . . . . . . . . . . . . Na2S2O3 3) This oxidation is carried out at room temperature in
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DM140-SC the dark during 30 minutes :
Unit of meas . . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL I2 + HPO32- + 3 OH - = 2I- + PO43- + 2 H2O
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . DYN
∆E(set)[mV] . . . . . . . . . 8.0
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
.
.
.
.
.
.
.
.
Relative
0.5
Procedure
∆V(max) [%buVol]. . . . . . 2.5
Measure mode . . . . . . . . . . EQU • The orthophosphite concentration is determined by
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 3.0 an iodometric back titration.
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 • The iodine concentration is determined by a simi-
Threshold . . . . . . . . . . . 150.0
EQP range . . . . . . . . . . . Yes lar method as 067. The result (mmol) is stored as
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . -1000.0 auxiliary value H3 and used for the back-titration.
Maximum volume [mL] . . . . . . . 30.0
Termination after n EQPs . . . . Yes • The sample is acidified with 20 mL 2 mol/L acetic
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard acid immediately before titration.
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
Na2HPO3
R1=(H3-Q1)*C1/U
• The iodine excess is then titrated with method 067.
Constant . . . . . . . . . . . . . . C1=125.9589/z
Result unit . . . . . . . . . . . . g/L • If the orthophosphite concentration exceeds the lim-
Decimal places . . . . . . . . . . . 2
Calculation it of 200 g/L an instruction is displayed.
Result name . . . . . . . . . . . . NaH2PO3
Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U
Constant . . . . . . . . . . . . . . C2=103.9768/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 Nickel content of different baths
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
H3PO3
R3=(H3-Q1)*C3/U
Bath n Content/ g/L srel/%
Constant . . . . . . . . . . . . . . C3=81.9947/z
Result unit . . . . . . . . . . . . g/L 28/10 A 3 189.00 0.158
Decimal places . . . . . . . . . . . 2
Instruction 28/10 B 8 189.66 0.103
Instruction . . . . . . . . . . . . CHECK CONCENTRATION
> . . . . . . . . . . . . . . . . . OF PHOSPHITE G601 6 184.26 0.121
> . . . . . . . . . . . . . . . . .
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>200 Disposal
Record
Output unit . . . . . . . . . . . . Printer Nickel solutions: special waste
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
E-V curve
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Standard deviation s . . . . . . . . Yes
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77. Author: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 19/100
METTLER TOLEDO
ALL RESULTS
STATISTICS
Number results R1 n = 3
Mean value x = 0.9598 mol/L HAc content
Standard deviation s = 0.00824 mol/L HAc content
Rel. standard deviation srel = 0.859 %
STATISTICS
Number results R2 n = 3
Mean value x = 0.9862 mol/L H3PO4 content
Standard deviation s = 0.00300 mol/L H3PO4 content
Rel. standard deviation srel = 0.304 %
STATISTICS
Number results R3 n = 3
Mean value x = 0.4429 mol/L HNO3 content
Standard deviation s = 0.00384 mol/L HNO3 content
Rel. standard deviation srel = 0.867 %
Page 20/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method Mix HAc+HNO3+H3PO4
Version 16-Mar-1999 17:18 • This titration procedure includes four steps:
Title 1. HNO3 = H+ + NO3-
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . Mix
. . . HAc+HNO3+H3PO4 2. H3PO4 = H+ + H2PO4-
Date/time . . . . . . . . . .
Sample
. . . 21-Nov-1991 12:44
3. HAc = H+ + Ac-
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Mix. Acid
Fixed volume 4. H2PO4 -
= H+ + HPO42-
Volume [mL] . . . . . . . . . . . 1.0
Molar mass M . . . . . . . . . . . . 100
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . . . . . ST20A Due to the little difference between the pKa-
Pump . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O value of HNO3 (pKa=approx. -1.3) and H3PO4
Volume [mL] . . . . . . . . . 50.0
Stir . . . . . . . . . . . . . No (pKa1=2.12), the first two steps can not be dis-
Pump . . . . . . . . . . . . . . No
Rinse . . . . . . . . . . . . . . Yes tinguished. Therefore only three potential
Solvent . . . . . . . . . . . H2O
Volume [mL] . . . . . . . . . 10.0 jumps can be seen on the titration curve.
Conditioning . . . . . . . . . . No
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50 • A sample changer ST20A is used in this meth-
Time [s] . . . . . . . . . . . . . . 10
EQP titration od for a fully automatic procedure. The meth-
Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH od can be easily modified for manual opera-
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DG111 tion: enter "Stand 1" as titration stand in the
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . to volume function SAMPLE.
Volume [mL] . . . . . . . . . . . 2.5
Wait time [s] . . . . . . . . . . 0
Titrant addition . . . . . . . . . . Dynamic
∆E(set)[mV]
∆V(min)[mL]
. . . . . . .
. . . . . . .
.
.
.
.
.
.
8.0
0.02
Disposal
∆V(max)[mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 1.0 Neutralization with hydrochloric acid.
∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . . 2.0
t(max) [s] . . . . . . . . . . . 10.0
Recognition
Threshold . . . . . . . . . . . . 17.0
Other titrators
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No DL50 Graphix, DL53/DL55, DL70ES, DL77.
Tendency . . . . . . . . . . . . None
Termination
at maximum volume [mL] . . . . . 40.0
at potential . . . . . . . . . . No
at slope . . . . . . . . .
after number EQPs . . . . .
.
.
.
.
.
.
No
Yes
E-V curve
n = . . . . . . . . . . . . . 3
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . No
Calculation
Formula . . . . . . . . . . . . . . R1=Q2*C1/m
Constant . . . . . . . . . . . . . . C1=1/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mol/L
Result name . . . . . . . . . . . . HAc content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=Q3*C2/m
Constant . . . . . . . . . . . . . . C2=1/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mol/L
Result name . . . . . . . . . . . . H3PO4 content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=(Q1-Q3)*C3/m
Constant . . . . . . . . . . . . . . C3=1/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mol/L
Result name . . . . . . . . . . . . HNO3 content
Statistics . . . . . . . . . . . . . Yes
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . No
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . No
∆E/∆V - V curve . . . . . . . . . . No
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Author: Li Pei
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 21/100
METTLER TOLEDO
M152 Nitric, acetic and phosphoric acid mixture: large excess of phosphoric acid
ALL RESULTS
1 0.5102 g
R1 = 3.0723 % HNO3 content
R2 = 12.2359 % HAc content
R3 = 70.9786 % H3PO4 content
2 0.5199 g
R1 = 3.0858 % HNO3 content
R2 = 12.0854 % HAc content
R3 = 70.8494 % H3PO4 content
3 0.518 g
R1 = 2.9778 % HNO3 content
R2 = 11.9648 % HAc content
R3 = 70.9050 % H3PO4 content
4 0.5373 g
R1 = 3.1480 % HNO3 content
R2 = 11.8686 % HAc content
R3 = 70.7380 % H3PO4 content
5 0.5176 g
R1 = 3.0152 % HNO3 content
R2 = 11.7205 % HAc content
R3 = 70.7452 % H3PO4 content
6 0.5078 g
R1 = 3.0452 % HNO3 content
R2 = 11.6033 % HAc content
R3 = 70.6551 % H3PO4 content
STATISTICS
Number results R1 n = 6
Mean value x = 3.0574 % HNO3 content
Standard deviation s = 0.05917 % HNO3 content
Rel. standard deviation srel = 1.935 %
STATISTICS
Number results R2 n = 6
Mean value x = 11.9131 % HAc content
Standard deviation s = 0.23308 % HAc content
Rel. standard deviation srel = 1.957 %
STATISTICS
Number results R3 n = 6
Mean value x = 70.8119 % H3PO4 content
Standard deviation s = 0.12031 % H3PO4 content
Rel. standard deviation srel = 0.170 %
Page 22/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 2.2 EQP Titration
Version 07/17/2000 13:59
Title • This titration procedure includes four steps:
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . 2.2
. . . EQP Titration 1. HNO3 = H+ + NO3-
Date/time . . . . . . . . . .
Sample
. . . 07/17/2000 13:59
2. H3PO4 = H+ + H2PO4-
=
Sample ID . . . . . . . . . . . . .
Entry type . . . . . . . . . . . . . Weight 3. HAc H+ + Ac-
=
Lower limit [g] . . . . . . . . . 0.4
Upper limit [g] . . . . . . . . . 0.6 4. H2PO4- H+ + HPO42-
Molar mass M . . . . . . . . . . . . 98
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . ST20A
Pump . . . . . . . . . . . . . . Yes Due to the little difference between the pKa-value
Solvent . . . . . . . . . . . H2O
Volume [mL] . . . . . . . . . 50.0 of HNO3 and H3PO4 ,the first two steps can not be
Stir . . . . . . . . . . . . . No
Pump . . . . . . . . . . . . . . No distinguished. Therefore only three potential jumps
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O can be seen on the titration curve.
Volume [mL] . . . . . . . . . 20.0
Conditioning . . . . . . . . . . Yes
Time [s] . . . . . . . .
Interval . . . . . . . .
.
.
.
.
.
.
20
1 • The two potential jumps are evaluated at potential
Rinse . . . . . . . . . . . . No
Temperature sensor . . . . . . . . . Manual
values of pH 3.75 and 5.5 (see evaluation). These
Stir
Speed [%] . . . . . . . . . . . . . 50
values are determined by a trial titration. From the
Time [s] . . . . . . . . . . .
EQP titration
. . . 10 table of measured values the pH values correspond-
Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH
ing to the potential jumps can be easily determined.
Concentration [mol/L] . . . . . . 1.0 The values are then used for sample analysis.
Sensor . . . . . . . . . . . . . DG111
Unit of meas. . . . . . . . . . . pH Note that these values depend on the concentration
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 3 of the sample and on sample preparation. Thus, it
Wait time [s] . . . . . . . . . . 10
Titrant addition . . . . . . . . . . Dynamic is necessary to first determine the potential values
∆E(set)[mV] . . . . . . . . . . 10.0
∆V(min)[mL] . . . . . . . . . . 0.005 for any other mixture.
∆V(max)[mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.3
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
.
.
.
.
.
.
2.0
5.0
Disposal
t(max) [s] . . . . . . . . . . . 52.0
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
.
.
.
.
.
.
6.0
No
Neutralization with hydrochloric acid.
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . None
Termination
at maximum volume [mL] . . . . . 12.0 Other titrators
at potential . . . . . . . . . . Yes
Potential [mV, pH,..] . . . . 10.5
at slope . . . . . . . . . . . . No DL50 Graphix, DL53/DL55, DL70ES, DL77.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . .
comb. termination criteria
.
.
.
.
.
.
1
Yes
E-V curve
Evaluation
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . Yes
Pot. 1 [mV, pH,..] . . . . . . 3.75
Potential 2 . . . . . . . . . . . Yes
Pot. 2 [mV, pH,..] . . . . . . 5.5
Stop for reevaluation . . . . . . No
Calculation
Formula . . . . . . . . . . . . . . R=(QP1-(Q-QP2))*C/m
Constant . . . . . . . . . . . . . . C=63.01/(10*z)
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . HNO3 content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=(QP2-QP1)*C2/m
Constant . . . . . . . . . . . . . . C2=60.05/(10*z)
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . HAc content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=(Q-QP2)*C3/m
Constant . . . . . . . . . . . . . . C3=M/(10*z)
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . H3PO4 content
Statistics . . . . . . . . . . . . . Yes
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No Author: Lin Yau Yeng (YY)
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 23/100
METTLER TOLEDO
M153 Nitric, acetic and phosphoric acid mixture: concentrations below 0.3%
RESULTS
STATISTICS
Number results R1 n = 3
Mean value x = 0.0940 % Nitric Acid
Standard deviation s = 0.001711 % Nitric Acid
Rel. standard deviation srel = 1.821 %
STATISTICS
Number results R2 n = 3
Mean value x = 0.1168 % Acetic Acid
Standard deviation s = 0.001026 % Acetic Acid
Rel. standard deviation srel = 0.878 %
STATISTICS
Number results R3 n = 3
Mean value x = 0.2509 % Phosphoric
Standard deviation s = 0.000804 % Phosphoric
Rel. standard deviation srel = 0.321 %
Page 24/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method Y021 Mixed Acids-HNO3,H3PO4,HAc • This titration procedure includes four steps:
Version Apr/23/1999 10:34 am
1. HNO3 = H+ + NO3-
Title
Method ID . . . . . . . . . . . . . Y021 2. H3PO4 = H+ + H2PO4-
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . Mixed Acids-HNO3,H3PO4,HAc
. . . . Apr/23/1999 10:34 am 3. HAc = H+ + Ac-
Sample
Number samples . . . . . . . . . . 3 4. H2PO4 -
= H+ + HPO42-
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
10.0 Due to the little difference between the pKa-value
Molar mass M . . . . . . . . . . . . 98 of HNO3 and H3PO4 , the first two steps can not be
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . . . . . . Manual distinguished. Therefore only three potential jumps
Stir
Speed [%] . . . . . . . . . . . . . 50 can be seen on the titration curve.
Time [s] . . . . . . . . . . . . . . 10
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
NaOH
0.1 • The potential jumps are evaluated by means of con-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DG111-SC
mV
trol ranges. To set the optimum values for the con-
Titration mode . . . . . . .
Predispensing 1 . . . . .
.
.
.
.
.
.
.
.
EQP
mL
trol ranges, a trial titration must be first performed.
Volume [mL] . . . . . . . . . 0 From the table of measured values the appropriate
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0 control ranges can be selected and stored in the
Limits ∆V . . . . . . . . . . Absolute
∆V(min) [mL] . . . . . . . 0.05 method.
∆V(min) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU Note that these values depends on the concentra-
∆E [mV] . . . . . . .
∆t [s] . . . . . . .
.
.
.
.
.
.
.
.
0.2
1.0
tion of the sample and on sample preparation. Thus,
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
3.0
30.0
it is necessary to first determine these values for
Threshold . . . . . . . . . . . . 40.0 any other acid mixture.
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 4
Evaluation procedure . .
Calculation
. . . . Standard
Disposal
Result name . . . . . . . . . . . . Nitric Acid
Formula . . . . . . . . . . . . . . R=(Q-Q(EPOT<-100))*C/U
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C=63/(10*z)
%
Neutralization with hydrochloric acid.
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . Acetic Acid
Formula . . . . . . . . . . . . . . R2=Q(100>EPOT>-80)*C2
Constant . . . . . . . . . . . . . . C=60/(U*10*z)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . Phosphoric E-V curve
Formula . . . . . . . . . . . . . . R3=Q(EPOT<-100)*C3/U
Constant . . . . . . . . . . . . . . C=M*3/(10*3)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 4
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL77. Author: Lin Yau Yeng (YY)
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 25/100
METTLER TOLEDO
Page 26/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method WS2 HCl/HOAc/NH4Cl
Version Sep/10/1999 9:49 am
Title
• A mixture of three different acids (hydrochlo-
Method ID . . . . . . . . .
Title . . . . . . . . . . .
. . . . WS2
. . . . HCl/HOAc/NH4Cl
ric acid, acetic acid and ammonium chloride)
Date/time . . . . . . . . .
Sample
. . . . Sep/10/1999 9:49 am
with clear different acid dissociation constant
Number samples . . . . . . .
Titration stand . . . . . .
.
.
.
.
.
.
.
.
6
ST20 1
(pKa = -10, 4.75, and 9.25, respectively) is ti-
Entry type . . . . . . . . .
Lower limit [mL] . . . .
.
.
.
.
.
.
.
.
Volume U
0.5
trated with 0.1 M NaOH.
Upper limit [mL] . . . . . . . . 2.5
ID1 . . . . . . . . . . . . . . . . Serie2
Molar mass M . . . . . . . . . . . . 36.46
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . .
Stir
. . . . Manual
• The mixture is prepared by adding 1 mL 0.1
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 20
mol/L of each acid soution into the titration
Titration
Titrant . . . . . . . . . . . . . . NaOH
beaker. The mixture is diluted with 40 mL
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DG111-SC
deionized water before titration.
Unit of meas. . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EQP
Titrant addition . . . . . . . . DYN
dE(set) [mV] . . . . . . . . . 8.0
Limits dV . . . . . .
dV(min) [mL] . . .
.
.
.
.
.
.
.
.
Absolute
0.03
• Reactions:
dV(max) [mL] . . .
Measure mode . . . . . .
.
.
.
.
.
.
.
.
0.1
EQU
Dominating reaction in the pH-range 2.8-5.0:
dE [mV] . . . . . . .
dt [s] . . . . . . . .
.
.
.
.
.
.
.
.
0.5
1.0
HCl + NaOH = Na + + Cl - + H 2 O
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . .
Maximum volume [mL] . . .
.
.
.
.
.
.
.
.
2.2
4.0
Dominating reaction in the pH-range 5.0-9.0:
Evaluation procedure . .
Stop for reevaluation . .
.
.
.
.
.
.
.
.
Standard
Yes
CH3COOH + NaOH = CH3COO- + Na+ + H2O
Condition . . . . . . . . . . neq=0
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
HCl
R1=Q1*C1/U
Dominating reaction in the pH-range 9.0-11.5:
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C1=M/(10*z)
mg/L
NH4Cl + NaOH = Na+ + Cl- + NH3 + H2O
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . HOAc
Formula . . . . . . . . . . . . . . R2=Q2*C2/U
Constant . . . . . . . . . . . . . . C2=60.0/(10*z)
Result unit . . . . . . . . . . . . mg/L
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
NH4Cl
R3=Q3*C3/U Disposal
Constant . . . . . . . . . . . . . . C3=53.49/(10*z)
Result unit . . . . . . . . . . . . mg/L
Decimal places . . . . . . . . . . . 3
Record Neutralization with hydrochloric acid.
Output unit . . . . . . . . . . . . Printer
Results last sample . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
dE/dV - V curve . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 20.0
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL70ES. Authors: H.-J. Muhr, E. Renaud Gueletti, J.Zarske
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 27/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 3
Mean value x = 48.99 % Phosphoric
Standard deviation s = 0.088515 % Phosphoric
Rel. standard deviation srel = 0.181 %
Page 28/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method hpo4 H2SO4+H3PO4 in Polstar • Sample preparation:
Version 21-02-1994 10:15
1 mL polishing bath is first diluted with water
Title (1:10). Again, 1 mL of the diluted solution is add-
Method ID . . . . . . . . . . . . . WS2
Title . . . . . . . . . . . . . . . H2SO4+H3PO4 in Polstar
ed into the titration beaker together with 50 mL
Date/time . . . . . . . . .
Sample
. . . . 21-02-1994 10:15 deionized water.
Number samples . . . . . . . . . . . 3
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Weight m • Sulfuric and phosphoric acid can dissociate two
Lower limit [g] . . . . . . . . . 0.0
Upper limit [mL] . . . . . . . . 2.0 protons H+ (sulfuric acid, H2SO4) and three pro-
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 98 tons H+ (phosphoric acid, H3PO4), respectively.
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . . . . . . Manual The dissociation constants pKa of H2SO4 are:
Stir
Speed [%] . . . . . . . . . . . . . 50 pKa1 = approx. -3,
Time [s] . . . . . . . . . . . . . . 10
Titration pKa2 = 1.92.
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
NaOH
0.5
Sulfuric acid is a strong acid that dissociates com-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DG111-SC
mV
pletely in water.
Titration mode . . . . . . .
Predispensing 1 . . . .
.
.
.
.
.
.
.
.
EQP
mL
The dissociation constants pKa of H3PO4 are:
Volumen [mL] . . . . . . . . 0.1 pKa1 = 2.12
Titrant addition . . . . . . . . DYN
dE(set) [mV] . . . . . . . . . 8.0 pKa2 = 7.21
Limits dV . . . . . . . . . . Absolute
dV(min) [mL] . . . . . . . 0.05 pKa3 = 12.67
dV(max) [mL] . . . . . . . 0.5
Measure mode . . . . . . . . . . EQU In aqueous solution only the first two dissociation
dE [mV] . . . . . . .
dt [s] . . . . . . . .
.
.
.
.
.
.
.
.
0.5
1.0
steps of phosphoric acid can be monitored, while
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
2.0
20.0
the third one is too weak .
Threshold . . . . . . . . . . . . 50.0
Maximum volume [mL] . . . . . . . 30.0
Termination after n EQPs . . . . Yes Based on the pK-values of the two acids in water,
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard the following reactions can be given for the two
Calculation
Result name . . . . . . . . . . . . Phosphoric EQPs found during titration:
Formula . . . . . . . . . . . . . . R1=Q2*C1/m
Constant . . . . . . . . . . . . . . C1=98/(10*z)
Result unit . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
%
2
1st EQP:
Calculation
Result name . . . . . . . . . . . . Sulfuric
H2SO4 + NaOH = Na+ + HSO4- + H2O
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R2=((Q1*2)-(Q1+Q2))*C2
C2=98/(10*z)
HSO4- + NaOH = Na + + SO 4 2- + H 2O
Result unit . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
%
2
H3PO4 + NaOH = H2PO4- + Na+ + H2O
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes 2nd EQP:
=
Rel. standard deviation srel . . . . Yes
Record H2PO4- + NaOH HPO42- + Na+ + H2O
Output unit . . . . . . . . . . . . Printer
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Disposal
Volume [mL] . . . . . . . . . . . . 20.0
E-V curve
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Authors: Application Laboratory MT-Germany
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 29/100
METTLER TOLEDO
RESULTS
Page 30/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method A001 Borsäure • Sample preparation:
Version 14-Nov-1989 12:28
200g mannitol are dissolved in 1 L volumetric flask
Title with deion. water.
Method ID . . . . . . . . . . . . . A001
Title . . . . . . . . . . . . . . . Borsäure
Boric acid can not be titrated directly in electro-
Date/time . . . . . . . . .
Sample
. . . . 14-Nov-1989 12:28 plating solution since it is a weak acid. To allow
Number samples . . . . . . . . . . . 1 titration, mannitol is added to the sample. Manni-
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Weight m tol forms a complex with boric acid giving in a me-
Lower limit [mL] . . . . . . . . 0.05
Upper limit [mL] . . . . . . . . 0.15 dium strong acidic compounds.
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 61.83
Equivalent number z . . . . . . . . 1
Stir
• A sample changer ST20A can be used in this meth-
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
od for a fully automatic procedure. The method
Titration can be easily modified for automatic operation:
Titrant . . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . . 0.1 enter "ST20 1" as titration stand in the function
Sensor . . . . . . . . . . . . . . . DG115-SC
Unit of meas. . . . . . . . . . . . mV SAMPLE.
Titration mode . . . . . . . . . . . EP
Predispensing . . . . . . . . . mL
Volume [mL] . . . . . . . . . 1.0
Titrant addition . . . . . . . . Dynamic
• CAUTION: Hydrofluoric acid is poisonous! Work
∆E(set) [mV] . . . . .
∆V(min) [mL] . . . . .
.
.
.
.
.
.
.
.
8.0
0.02
in a fume hood, wear safety goggles and gloves.
∆V(max) [mL] . . . . . . . . . 0.1
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 0.5
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
2.0
20.0
Disposal
Endpoint mode . . . . . . . . . . EPA Neutralization with hydrochloric acid.
Potential [mV,pH,...]. . . . . 0.0
Tendency . . . . . . . . . . . . Negative
Maximum volume [mL] . . . . . . . 10.0
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
mL HCl/HF
R=VEQ[1]
E-V curve:
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mL
Decimal places . . . . . . . . . . . 3 Titration of HCl/HF
Record
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Dispense
Titrant . . . . . . . . . . . . . . Mannitol
Concentration [mol/L] . . . . . . . 0.0
Volume [mL] . . . . . . . . . . . . 20.0
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60
Titration
Titrant . . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DG115-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL
Volumen [mL] . . . . . . . . 1.0
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Absolute
∆V(min) [mL]. . . . . . . . 0.02
∆V(max) [mL]. . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 1.0 Titration of boric acid
∆t [s] . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 20.0
Maximum volume [mL] . . . . . . . 10.0
Evaluation procedure . . . . . . Standard
Calculation
Result name . . . . . . . . . . . . mL Brsaeure
Formula . . . . . . . . . . . . . . R2=VEQ[2]
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mL
Decimal places . . . . . . . . . . . 3
Record
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Author: Dieter Rehwald
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 31/100
Note:
Sample: 1st titration: 0.5 g polishing bath Titrant: Potassium hydroxide, KOH
2nd titration: 1 g polishing bath c(NaOH) = 1.0 mol/L
Remarks
• HNO3-content:
Hydrofluoric acid (HF) and nitric acid (HNO3) are both strong acids in aqueous solution (dissocia-
tion constant pKa(HNO3) = -1.32 at 12.5°C; and pKa(HF) = 3.45), they dissociate completely. Since
the pKa values are close to each other, the two potential jumps can not be distinguished during
titration with a strong base in an aqueous solution: there is only one potential jump in the titration
curve.
To discriminate the two potential jumps, the solvent is replaced by acetone, where the difference in
pKa values of the two acids is large enough to separate them. The first EQP of the second titration
function corresponds to nitric acid. Further addition of sodium sulphate, a well-known drying agent
due to its hygroscopic property, allows the achievement of a complete anhydrous environment.
Page 32/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Titration
Titrant . . . . . . . . . . . . . . KOH
Method HF1 HF and HNO3 Content Concentration [mol/L] . . . . . . . 1.0
Version Dec/03/1998 11:25 am Sensor . . . . . . . . . . . . . . . InLab 429
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Title Predispensing 1 . . . . . . . . . mL
Method ID . . . . . . . . . . . . . HF1 Volume [mL] . . . . . . . . . 1.0
Title . . . . . . . . . . . . . . . HF and HNO3 Content Titrant addition . . . . . . . . DYN
Date/time . . . . . . . . . . . . . Dec/03/1998 11:25 am ∆E(set) [mV] . . . . . . . . . 8.0
Sample Limits ∆V . . . . . . . . . . Absolute
Number samples . . . . . . . . . . . 3 ∆V(min) [mL] . . . . . . . 0.02
Titration stand . . . . . . . . . . Stand 1 ∆V(max) [mL] . . . . . . . 0.5
Entry type . . . . . . . . . . . . . Weight m Measure mode . . . . . . . . . . EQU
Lower limit [mL] . . . . . . . . 0.0 ∆E [mV] . . . . . . . . . . . 0.5
Upper limit [mL] . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . 1.0
ID1 . . . . . . . . . . . . . . . . HNO3 t(min) [s] . . . . . . . . . . 3.0
Molar mass M . . . . . . . . . . . . 63.0129 t(max) [s] . . . . . . . . . . 30.0
Equivalent number z . . . . . . . . 1 Threshold . . . . . . . . . . . . 100.0
Temperature sensor . . . . . . . . . Manual Maximum volume [mL] . . . . . . . 20.0
Stir Termination after n EQPs . . . . Yes
Speed [%] . . . . . . . . . . . . . 50 n = . . . . . . . . . . . . . 1
Time [s] . . . . . . . . . . . . . . 30 Termination at slope . . . . . . Yes
Titration Slope [mV,pH,.../mL] . . . . . 50.0
Titrant . . . . . . . . . . . . . . KOH Combined termn criteria . . . . . Yes
Concentration [mol/L] . . . . . . . 1.0 Evaluation procedure . . . . . . Standard
Sensor . . . . . . . . . . . . . . . InLab 429 Steepest jump only . . . . . . . Yes
Unit of meas. . . . . . . . . . . . mV Stop for reevaluation . . . . . . Yes
Titration mode . . . . . . . . . . . EQP Condition . . . . . . . . . . neq=0
Predispensing 1 . . . . . . . . . mL Calculation
Volume [mL] . . . . . . . . . 1.0 Result name . . . . . . . . . . . . HNO3 Content
Titrant addition . . . . . . . . DYN Formula . . . . . . . . . . . . . . R2=Q[2]*C2/m
∆E(set) [mV] . . . . . . . . . 8.0 Constant . . . . . . . . . . . . . . C2=1/z
Limits ∆V . . . . . . . . . . Absolute Result unit . . . . . . . . . . . . mmol/g
∆V(min) [mL] . . . . . . . 0.02 Decimal places . . . . . . . . . . . 4
∆V(max) [mL] . . . . . . . 0.5 Record
Measure mode . . . . . . . . . . EQU Output unit . . . . . . . . . . . . Printer
∆E [mV] . . . . . . . . . . . 0.5 Result last sample . . . . . . . . . Yes
∆t [s] . . . . . . . . . . . . 1.0 Table of values . . . . . . . . . . Yes
t(min) [s] . . . . . . . . . . 3.0 E - V curve . . . . . . . . . . . . Yes
t(max) [s] . . . . . . . . . . 30.0 Statistics
Threshold . . . . . . . . . . . . 100.0 Ri (i=index) . . . . . . . . . . . . R2
Maximum volume [mL] . . . . . . . 20.0 Standard deviation s . . . . . . . . Yes
Termination after n EQPs . . . . Yes Rel. standard deviation srel . . . . Yes
n = . . . . . . . . . . . . . 1 Calculation
Termination at slope . . . . . . Yes Result name . . . . . . . . . . . . HNO3 Content
Slope [mV,pH,.../mL] . . . . . 50.0 Formula . . . . . . . . . . . . . . R3=R2*C3/m
Combined termn criteria . . . . . Yes Constant . . . . . . . . . . . . . . C3=63.0129/(10*z)
Evaluation procedure . . . . . . Standard Result unit . . . . . . . . . . . . %
Steepest jump only . . . . . . . Yes Decimal places . . . . . . . . . . . 3
Stop for reevaluation . . . . . . Yes Calculation
Condition . . . . . . . . . . neq=0 Result name . . . . . . . . . . . . HF Content
Calculation Formula . . . . . . . . . . . . . . R4=(R1-R2)*C4
Result name . . . . . . . . . . . . Total acid Constant . . . . . . . . . . . . . . C4=20.0063/(10*z)
Formula . . . . . . . . . . . . . . R=Q*C/m Result unit . . . . . . . . . . . . %
Constant . . . . . . . . . . . . . . C=1/z Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . mmol/g Record
Decimal places . . . . . . . . . . . 4 Output unit . . . . . . . . . . . . Printer
Record All results . . . . . . . . . . . . Yes
Output unit . . . . . . . . . . . . Printer
Result last sample . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Remarks
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Sample
Number samples . . . . . . . . . . . 3 • A sample changer ST20A can be used in this
Titration stand . . . . . . . . .
Entry type . . . . . . . . . . . .
.
.
Stand 1
Weight m method for a fully automatic procedure. The
Lower limit [mL] . . . . . . .
Upper limit [mL] . . . . . . .
.
.
0.0
1.0 method can be easily modified for automatic
ID1 . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . .
.
.
HF
20.0063 operation: enter "ST20 1" as titration stand in
Equivalent number z . . . . . . .
Temperature sensor . . . . . . . .
.
.
1
Manual the function SAMPLE.
Instruction
Attach sample with sodium sulphate
added and acetone as a solvent
Stir • CAUTION: HF is a very strong acid and it etch-
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60 es glass. Wear gloves and safety goggles.
Disposal
ALL RESULTS
1 HCl/HNO3 1.011 g
R1 = 29.291 % mmol H+
ALL RESULTS
1 HCl/HNO3 1.011 g
R1 = 29.291 % HCl content
R2 = 2.676 % HNO3
Page 34/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method jud3 Method jud2
Method jud3 Total acid cont (HCl+HNO3) Method jud2 HCl det. with AgNO3
Version 08/08/2000 12:20 Version 08/08/2000 12:49
Title Title
Method ID . . . . . . . . . . . . . jud3 Method ID . . . . . . . . . . . . . jud2
Title . . . . . . . . . . . . . Total acid cont Title . . . . . . . . . . . . . HCl det. with AgNO3
(HCl+HNO3) Date/time . . . . . . . . . . . . . 08/08/2000 12:49
Date/time . . . . . . . . . . . . . 08/08/2000 12:20 Sample
Sample Sample ID . . . . . . . . . . . . . HCl/HNO3
Sample ID . . . . . . . . . . . . . HCl/HNO3 Entry type . . . . . . . . . . . . . Weight
Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02
Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0
Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 36.45
Molar mass M . . . . . . . . . . . . 100 Equivalent number z . . . . . . . . 1
Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1
Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . Manual
Temperature sensor . . . . . . . . . Manual Stir
Stir Speed [%] . . . . . . . . . . . . . 50
Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10
Time [s] . . . . . . . . . . . . . . 10 EQP titration
EQP titration Titrant/Sensor
Titrant/Sensor Titrant . . . . . . . . . . . . . AgNO3
Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0
Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DM141
Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . mV
Unit of meas. . . . . . . . . . . pH Predispensing . . . . . . . . . . . No
Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic
Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0
∆E(set)[mV] . . . . . . . . . . 4.0 ∆V(min)[mL] . . . . . . . . . . 0.02
∆V(min)[mL] . . . . . . . . . . 0.01 ∆V(max)[mL] . . . . . . . . . . 0.2
∆V(max)[mL] . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled
Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5
∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0
t(max) [s] . . . . . . . . . . . 30.0 Recognition
Recognition Threshold . . . . . . . . . . . . 1000.0
Threshold . . . . . . . . . . . . 50.0 Steepest jump only . . . . . . . No
Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No
Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . None
Tendency . . . . . . . . . . . . None Termination
Termination at maximum volume [mL] . . . . . 10.0
at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No
at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No
at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes
after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1
n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No
comb. termination criteria . . . No Evaluation
Evaluation Procedure . . . . . . . . . . . . Standard
Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No
Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes
Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0
Condition . . . . . . . . . . neq=0 Calculation
Calculation Formula . . . . . . . . . . . . . . R=Q*C/m
Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . C=M/(10*z)
Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3
Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . %
Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . HCl content
Result name . . . . . . . . . . . . H+ Statistics . . . . . . . . . . . . . No
Statistics . . . . . . . . . . . . . No Calculation
Calculation Formula . . . . . . . . . . . . . . R2=(H5-Q)*C2/m
Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . C2=63.01/(10*z)
Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3
Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . %
Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . HNO3
Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . Yes
Statistics . . . . . . . . . . . . . No Calculation
Auxiliary value Formula . . . . . . . . . . . . . .
ID . . . . . . . . . . . . . . . . . Total acid Constant . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . H5=R Decimal places . . . . . . . . . . . 0
Report Result unit . . . . . . . . . . . .
Output . . . . . . . . . . . . . . . Printer Result name . . . . . . . . . . . .
Results . . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes Report
Raw results . . . . . . . . . . . . Yes Output . . . . . . . . . . . . . . . Printer
Table of measured values . . . . . . Yes Results . . . . . . . . . . . . . . No
Sample data . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes Table of measured values . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No Sample data . . . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No E - V curve . . . . . . . . . . . . Yes
E - t curve . . . . . . . . . . . . No ∆E/∆V - V curve . . . . . . . . . . Yes
V - t curve . . . . . . . . . . . . No ∆2E/∆V2 - V curve . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
Remarks V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
.
.
.
.
No
No
ALL RESULTS
1 NH3/H2O2 0.662 g
R1 = 3.484 % NH3 Content
ALL RESULTS
1 NH3/H2O2 0.662 g
R1 = 0.936 % H2O2 content
Page 36/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method amm1 Method hydr1
Method amm1 Back titration of NH3 Method hydr1 H2O2 determination
Version 08/11/2000 13:29 Version 08/11/2000 12:50
Title Title
Method ID . . . . . . . . . . . . . amm1 Method ID . . . . . . . . . . . . . hydr1
Title . . . . . . . . . . . . . Back titration of NH3 Title . . . . . . . . . . . . . H2O2 determination
Date/time . . . . . . . . . . . . . 08/11/2000 13:29 Date/time . . . . . . . . . . . . . 08/11/2000 12:50
Sample Sample
Sample ID . . . . . . . . . . . . . NH3/H2O2 Sample ID . . . . . . . . . . . . . NH3/H2O2
Entry type . . . . . . . . . . . . . Weight Entry type . . . . . . . . . . . . . Weight
Lower limit [g] . . . . . . . . . 0.02 Lower limit [g] . . . . . . . . . 0.02
Upper limit [g] . . . . . . . . . 2.0 Upper limit [g] . . . . . . . . . 2.0
Molar mass M . . . . . . . . . . . . 17 Molar mass M . . . . . . . . . . . . 34.02
Equivalent number z . . . . . . . . 1 Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Temperature sensor . . . . . . . . . Manual
Dispense Stir
Titrant . . . . . . . . . . . . . . HNO3 Speed [%] . . . . . . . . . . . . . 50
Concentration [mol/L] . . . . . . . 2.0 Time [s] . . . . . . . . . . . . . . 10
Volume [mL] . . . . . . . . . . . . 4.5 EQP titration
Stir Titrant/Sensor
Speed [%] . . . . . . . . . . . . . 50 Titrant . . . . . . . . . . . . . 1/5 KMnO4
Time [s] . . . . . . . . . . . . . . 10 Concentration [mol/L] . . . . . . 0.1
EQP titration Sensor . . . . . . . . . . . . . DM140
Titrant/Sensor Unit of meas. . . . . . . . . . . mV
Titrant . . . . . . . . . . . . . NaOH Predispensing . . . . . . . . . . . No
Concentration [mol/L] . . . . . . 1.0 Titrant addition . . . . . . . . . . Dynamic
Sensor . . . . . . . . . . . . . DG111 ∆E(set)[mV] . . . . . . . . . . 8.0
Unit of meas. . . . . . . . . . . pH ∆V(min)[mL] . . . . . . . . . . 0.02
Predispensing . . . . . . . . . . . No ∆V(max)[mL] . . . . . . . . . . 0.2
Titrant addition . . . . . . . . . . Dynamic Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E(set)[mV] . . . . . . . . . . 8.0 ∆E [mV] . . . . . . . . . . . . . 0.5
∆V(min)[mL] . . . . . . . . . . 0.02 ∆t [s] . . . . . . . . . . . . . 1.0
∆V(max)[mL] . . . . . . . . . . 0.2 t(min) [s] . . . . . . . . . . . 3.0
Measure mode . . . . . . . . . . . . Equilibrium controlled t(max) [s] . . . . . . . . . . . 15.0
∆E [mV] . . . . . . . . . . . . . 0.5 Recognition
∆t [s] . . . . . . . . . . . . . 1.0 Threshold . . . . . . . . . . . . 2000.0
t(min) [s] . . . . . . . . . . . 3.0 Steepest jump only . . . . . . . No
t(max) [s] . . . . . . . . . . . 30.0 Range . . . . . . . . . . . . . . No
Recognition Tendency . . . . . . . . . . . . Positive
Threshold . . . . . . . . . . . . 100.0 Termination
Steepest jump only . . . . . . . No at maximum volume [mL] . . . . . 8.0
Range . . . . . . . . . . . . . . No at potential . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive at slope . . . . . . . . . . . . No
Termination after number EQPs . . . . . . . . Yes
at maximum volume [mL] . . . . . 10.0 n = . . . . . . . . . . . . . 1
at potential . . . . . . . . . . No comb. termination criteria . . . No
at slope . . . . . . . . . . . . No Evaluation
after number EQPs . . . . . . . . Yes Procedure . . . . . . . . . . . . Standard
n = . . . . . . . . . . . . . 1 Potential 1 . . . . . . . . . . . No
comb. termination criteria . . . No Potential 2 . . . . . . . . . . . No
Evaluation Stop for reevaluation . . . . . . Yes
Procedure . . . . . . . . . . . . Standard Condition . . . . . . . . . . neq=0
Potential 1 . . . . . . . . . . . No Calculation
Potential 2 . . . . . . . . . . . No Formula . . . . . . . . . . . . . . R=Q*C/m
Stop for reevaluation . . . . . . Yes Constant . . . . . . . . . . . . . . C=M/(10*z)
Condition . . . . . . . . . . neq=0 Decimal places . . . . . . . . . . . 3
Calculation Result unit . . . . . . . . . . . . %
Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m Result name . . . . . . . . . . . . H2O2 content
Constant . . . . . . . . . . . . . . C=M/(10*z) Statistics . . . . . . . . . . . . . Yes
Decimal places . . . . . . . . . . . 3 Calculation
Result unit . . . . . . . . . . . . % Formula . . . . . . . . . . . . . .
Result name . . . . . . . . . . . . NH3 Content Constant . . . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Decimal places . . . . . . . . . . . 0
Calculation Result unit . . . . . . . . . . . .
Formula . . . . . . . . . . . . . . Result name . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Statistics . . . . . . . . . . . . . No
Decimal places . . . . . . . . . . . 0 Calculation
Result unit . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Result name . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Decimal places . . . . . . . . . . . 0
Report Result unit . . . . . . . . . . . .
Output . . . . . . . . . . . . . . . Printer Result name . . . . . . . . . . . .
Results . . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes Report
Raw results . . . . . . . . . . . . No Output . . . . . . . . . . . . . . . Printer
Table of measured values . . . . . . Yes Results . . . . . . . . . . . . . . No
Sample data . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes Table of measured values . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No Sample data . . . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No E - V curve . . . . . . . . . . . . Yes
E - t curve . . . . . . . . . . . . No ∆E/∆V - V curve . . . . . . . . . . Yes
V - t curve . . . . . . . . . . . . No ∆2E/∆V2 - V curve . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Remarks
Disposal
1. Method amm1: det. of NH3 by back titration. The sample has to be classified as special waste.
2. Add 1 mL 10% HNO3 for peroxide determination
3. Method hydr1: determination of HCl by redox ti-
tration with 1/5 KMnO4. Other titrators
Please note that both methods can be resumed in a sin- DL50 Graphix, DL53/DL55, DL70ES, DL77.
gle method. Author: Judy Maag
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 37/100
METTLER TOLEDO
ALL RESULTS
1 HCl/H2O2 0.777 g
R1 = 1.188 % HCl Content
ALL RESULTS
1 HCl/H2O2 0.777 g
R1 = 2.075 % H2O2 content
Page 38/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method hcl1 Method hydr1
Method hcl1 Titration of HCl Method hydr1 H2O2 determination
Version 08/11/2000 14:01 Version 08/11/2000 14:03
Title Title
Method ID . . . . . . . . . . . . . hcl1 Method ID . . . . . . . . . . . . . hydr1
Title . . . . . . . . . . . . . Titration of HCl Title . . . . . . . . . . . . . H2O2 determination
Date/time . . . . . . . . . . . . . 08/11/2000 14:01 Date/time . . . . . . . . . . . . . 08/11/2000 14:03
Sample Sample
Sample ID . . . . . . . . . . . . . HCl/H2O2 Sample ID . . . . . . . . . . . . . HCl/H2O2
Entry type . . . . . . . . . . . . . Weight Entry type . . . . . . . . . . . . . Weight
Lower limit [g] . . . . . . . . . 0.02 Lower limit [g] . . . . . . . . . 0.02
Upper limit [g] . . . . . . . . . 2.0 Upper limit [g] . . . . . . . . . 2.0
Molar mass M . . . . . . . . . . . . 36.35 Molar mass M . . . . . . . . . . . . 34.02
Equivalent number z . . . . . . . . 1 Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Temperature sensor . . . . . . . . . Manual
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 Time [s] . . . . . . . . . . . . . . 10
EQP titration EQP titration
Titrant/Sensor Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH Titrant . . . . . . . . . . . . . 1/5 KMnO4
Concentration [mol/L] . . . . . . 1.0 Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DG111 Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . pH Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No Predispensing . . . . . . . . . . . No
Titrant addition . . . . . . . . . . Dynamic Titrant addition . . . . . . . . . . Dynamic
∆E(set)[mV] . . . . . . . . . . 8.0 ∆E(set)[mV] . . . . . . . . . . 8.0
∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(min)[mL] . . . . . . . . . . 0.02
∆V(max)[mL] . . . . . . . . . . 0.2 ∆V(max)[mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.5 ∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0 t(max) [s] . . . . . . . . . . . 15.0
Recognition Recognition
Threshold . . . . . . . . . . . . 100.0 Threshold . . . . . . . . . . . . 2000.0
Steepest jump only . . . . . . . No Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive Tendency . . . . . . . . . . . . Positive
Termination Termination
at maximum volume [mL] . . . . . 10.0 at maximum volume [mL] . . . . . 8.0
at potential . . . . . . . . . . No at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No comb. termination criteria . . . No
Evaluation Evaluation
Procedure . . . . . . . . . . . . Standard Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 Condition . . . . . . . . . . neq=0
Calculation Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) Constant . . . . . . . . . . . . . . C=M/(10*z)
Decimal places . . . . . . . . . . . 3 Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . % Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . HCl Content Result name . . . . . . . . . . . . H2O2 content
Statistics . . . . . . . . . . . . . Yes Statistics . . . . . . . . . . . . . Yes
Calculation Calculation
Formula . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
Calculation Calculation
Formula . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
Report Report
Output . . . . . . . . . . . . . . . Printer Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No Raw results . . . . . . . . . . . . Yes
Table of measured values . . . . . . Yes Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes ∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No ∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No ∆V/∆t - t curve . . . . . . . . . . No
Remarks Disposal
The sample to be classified as special waste.
1. Method hcl1: det. of HCl by direct titration.
2. Add 1 mL 10% HNO3 for peroxide determination
3. Method hydr1: determination of H2O2 by redox Other titrators
titration with 1/5 KMnO4. DL50 Graphix, DL53/DL55, DL70ES, DL77.
Note: the methods can be resumed in a single one. Author: Judy Maag
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 39/100
METTLER TOLEDO
n = 4 flat titration
curve
x 15.434
srel 0.66% DL40 Appl. no. 315
n = 5 INC = 0.1 mL
Threshold= 100mV/mL
x 99.542 ∆E = 0.5 mV
srel 0.05% ∆t = 3.0
DL40 Appl. no. 110
Page 40/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40001 Aluminium
Version 11/01/2001 16:30 Aluminium acidic bath (Elox bath)
Title
Method ID . . . . . . . . . . . . . 40001 • This acidic bath contains aluminium, sulfuric and
Title . . . . . . . . . . . . . Aluminium
Date/time . . . . . . . . . . . . . 11/01/2001 16:30 oxalic acid.
Sample
Sample ID . . . . . . . . . . . . . Al/H2SO4/C2O42- • The method was developed on the DL40 titrator
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . . . . . . 1.0 (see DL40 applications No. 3, 110, 315) and has
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
26.982
1
been adapted for the DL5x- and DL7x-titrators.
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50
Sample preparation
Time [s] . . . . . . . . . . . . . . 10
EQP titration 1) Add 20 mL deionized water to the sample.
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
ZnSO4
0.1
2) Add 20 mL buffer solution pH 4 to avoid formation
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
HgDM141
mV
of aluminium hydroxide.
Predispensing . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 5.0 3) 20 mL 0.1 mol/L EDTA are dispensed using the
Titrant addition . . . . . . . . . . INC
∆V [mL] . . . . . . . . . . . . . 0.3 auxiliary function "Dosing" of the titrator.
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 3.0 4) The sample beaker is heated to boiling during 10
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0 minutes since the complexation of aluminium with
Recognition
Threshold . . . . . . . . . . . . 25.0 EDTA is very slow at room temperature. Cover the
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
glass titration beaker during heating.
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . . . . . 20.0
5) Add three drops 0.05 mol/L Hg-EDTA
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 Procedure
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard • The aluminum concentration is determined by a
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No back titration of excess EDTA with zinc sulfate.
Stop for reevaluation . . . . . . Yes
Calculation
Condition . . . . . . . . . . neq=0 • A blank titration is performed before analysis. The
Formula . . . . . . . . . . . . . . R=(H1-Q)*C/m result (mmol) is stored as auxiliary value H1 and
Constant . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 3 used for the back-titration.
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Al Content
Yes
• The EDTA excess is titrated with method 40001.
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
Chemicals
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . • Buffer solution pH 4: Dissolve 120 mL glacial ace-
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No tic acid (i.e. 100%) and 54 g sodium acetate trihy-
Calculation
Formula . . . . . . . . . . . . . . drate in a 1 L flask. Add 10 mL 0.05 mol/L HgED-
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 TA, and dilute to 1 L with deionized water.
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No • 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
Report
Output . . . . . . . . . . . . . . . Printer
and 0.05 mol/L Hg-acetate are mixed together. This
Results . . . . . . . . . . .
All results . . . . . . . . .
.
.
.
.
.
.
No
Yes
solution is used as an indicator for the titration and
Raw results . . . . . . . . .
Table of measured values . . .
.
.
.
.
.
.
No
Yes
is dissolved into the buffer solution instead of add-
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
.
.
.
.
.
.
No
Yes
ing three drops for each sample.
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No Amalgamation of DM141 electrode (HgDM141)
∆V/∆t - t curve . . . . . . . . . . No
Results:
Results n srel Comments
Content Aluminum:
1.857 g/L 3 1.323%
Test solution:
Theoretical 49 g/L
content (g/L)
Content Aluminum:
2.347 g/L 5 1.233%
Theoretical
content (g) 2.3 g/L Al
Page 42/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 25002 Free acid + Al
Version 26/01/2001 15:46
• The method was developed on the DL25 titrator
Title
Method ID . . . . . . . . . . . . . 25002
and has been adapted for the DL5x-/7x-titrators.
Title . . . . . . . . . . . . . Free acid + Al
Date/time . . . . . . . . . . . . . 26/01/2001 15:46
Sample
Sample ID . . . . . . . . . . . . . H2SO4/Al
Procedure
Entry type . . . . . . . . . . . . . Fixed volume • The determination of free acid and aluminum in an
Volume [mL] . . . . . . . . . . . 2.0
Molar mass M . . . . . . . . . . . . 26.98 acidic aluminun bath is determined with a single
Equivalent number z . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1 titration using sodium hydroxide.
Temperature sensor . . . . . . . . . Manual
Stir • The titration curve gives three equivalence points:
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
EQP titration
Titrant/Sensor 1st EQP: Neutralization of free acid
Titrant . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . 1.0 H2SO4 + 2 NaOH = Na2SO4 + 2 H2O
Sensor . . . . . . . . . . . . . DG111
Unit of meas. . . . . . . . . . . As installed
Predispensing . . . . . .
Titrant addition . . . . .
.
.
.
.
.
.
.
.
.
.
No
Dynamic
2nd EQP: Precipitation of aluminum hydroxide
∆E(set) [mV] . . . . . . . . . . 4.0 Al2(SO4)3 + 6 NaOH = 2 Al(OH)3 + 2 H2O
∆V(min) [mL] . . . . . . . . . . 0.02
∆V(min) . . . . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . .
∆t [s] . . . . . . . .
.
.
.
.
.
.
.
.
.
.
0.5
1.0
3rd EQP: Dissolution of Al(OH)3
t(min) [s] . . . . . . . . . . . 3.0 Al(OH)3 + NaOH = Al(OH)4- + Na+
t(max) [s] . . . . . . . . . . . 30.0
Recognition
Threshold . . . . . . . . . . . . 4
Steepest jump only . .
Range . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
No
No
Literature
Tendency . . . . . . . . . . . . Positive
Termination • Application no. M531, in Application brochure 18,
at maximum volume [mL] . . . . . 4.0
at potential . . . . . . . . . . No "Standardization of Titrants", 2000.
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . No
Evaluation
Procedure . . . . . . .
Potential 1 . . . . . .
.
.
.
.
.
.
.
.
.
.
Standard
No Titration curves: standard solution
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0
Calculation
Formula . . . . . . . . . . . . . . R1=Q1*C1/m
Constant . . . . . . . . . . . . . . C1=98.07/2
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . H2SO4
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=Q2*C2/m
Constant . . . . . . . . . . . . . . C2=M/z
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Aluminum
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Neutralization with HCl, special waste
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Author: Roland Böhlen, MT-Switzerland
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 43/100
METTLER TOLEDO
Standard: ZnSO4
Results:
Page 44/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40002 Ni + Cd
Version 12/01/2001 15:50 • The method was developed on the DL40 titrator
Title (see DL40 applications No. 317) and has been
Method ID . . . . . . . . . . . . . 40002
Title . . . . . . . . . . . . . Ni + Cd adapted for the DL5x- and DL7x-titrators.
Date/time . . . . . . . . . . . . . 12/01/2001 15:50
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Ni/Cd
Fixed volume Sample preparation
Volume [mL] . . . . . . . . . . . 5.0
Molar mass M . . . . . . . . . . . . 112.41 A) Cadmium determination:
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 1) Add 10 mL buffer solution pH 10.
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50
2) Add 0.5 g dimethylglyoxime disodium salt to
Time [s] . . . . . . . . . . .
EQP titration
. . . 10
mask nickel ions.
Titrant/Sensor
Titrant . . . . . . . . . . . . . EDTA 3) Add 40 mL deionized water.
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . HgDM141 4) Add 3 drops 0.05 mol/L HgEDTA.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 1.0 B) Ni determination:
Titrant addition . . . . . . . . . . INC
∆V [mL] . . . . . . . . . . . . . 0.1 1) Add 10 mL buffer solution pH 10.
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
0.2
2.0
2) Add 40 mL deionized water.
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0 3) Add 3 drops 0.05 mol/L HgEDTA.
Recognition
Threshold . . . . . . . . . . . . 150
Steepest jump only . . . . . . . No
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Negative Procedure
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
20.0
No
• Cd content:
at slope . . . . . . . . .
after number EQPs . . . . .
.
.
.
.
.
.
No
Yes
1) Ni is masked with dimethylglyoxime disodium
n = . . . . . . . . . .
comb. termination criteria
.
.
.
.
.
.
1
No
salt. The sample is titrated with method 40002.
Evaluation
Procedure . . . . . . . . . . . . Standard
2) The Cd content is stored as auxiliary value H6.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . .
Condition . . . . . . .
.
.
.
.
.
.
Yes
neq=0
• Ni content:
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
1) EDTA forms complexes with both Ni and Cd.
Constant . . . . . . . . . . . . . . C=M/z 2) To distinguish both metal ions, the Cd content
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . g/L is accounted for as a blank value in the calcula-
Result name . . . . . . . . . . . . Cd Content
Statistics . . . . . . . . . . . . . Yes tion: R = (Q - H6)*C/m .
Calculation
Formula . . . . . . . . . . . . . . R2=Q 3) Since nickel is determined, C = M(Ni)/z, and
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3 therefore M = 58.59 .
Result unit . . . . . . . . . . . . mmol
Result name . . . . . . . . . . . . Cd Content
Statistics . . . . . . . . . . . . . Yes
Auxiliary value Chemicals
ID . . . . . . . . . . . . . . . . . mmol Cd
Constant . . . . . . . . . . . . . . H6=R2
Report • Buffer solution pH 10: 70 mL of concentrated am-
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No
monia solution (d=0.9 g/mL) and 70 g ammonium
All results . . . . . . . . .
Raw results . . . . . . . . .
.
.
.
.
.
.
Yes
No
chloride (or 110 g NH4NO3) are dissolved in a 1 L
Table of measured values . . .
Sample data . . . . . . . . .
.
.
.
.
.
.
Yes
No
flask with deionized water.
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No and 0.05 mol/L Hg-acetate are mixed together.
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Results:
RESULTS
STATISTICS
Number results R1 n = 3
Mean value x = 23.73 g/L Cadmium
Standard deviation s = 0.560119 g/L Cadmium
Rel. standard deviation srel = 2.361 %
Page 46/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method BL65 Cadmium im alk. Elektrolyt
Version 21-02-1994 9:48
Title
Sample preparation
Method ID . . . . . . . . . . . . . BL65
Title . . . . . . . . . . . . . . . Cadmium im alk.
1) The sample is diluted and then titrated with 0.1 M
Elektrolyt EDTA. No pH buffer is added, the bath is alkaline.
Date/time . . . . . . . . . . . . . 21-02-1994 9:48
Sample
Number samples . . . . . . . . . . . 3
2) Use a trituration 1:500 murexide: NaCl.
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume U 3) Add the indicator before starting analysis. Keep
Volume [mL] . . . . . . . . . . . 1.0
ID1 . . . . . . . . . . . . . . . . sample free of air bubbles during titration. Air
Molar mass M . . . . . . . . . . . . 112.40
Equivalent number z . . . . . . . . 1 bubbles and undissolved impurities affect with the
Temperature sensor . . . . . . . . . Manual
Stir photometric indication.
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 4) Adjust the DP660 at 1000 mV in deionised water
Titration
Titrant . . . . . . . . . . . . . . EDTA before starting titration (100% transmission).
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DP660
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . mL
Volume [mL] . . . .
Titrant addition . . . .
.
.
.
.
.
.
.
.
0.5
DYN
Titration
dE(set) [mV] . . . . . . . . . 8.0
Limits dV . . . . . . . . . . Absolute • Cd(II) ions forms complexes with the indicator
dV(min) [mL] . . . . . . . 0.05
dV(max) [mL] . . . . . . . 0.2 murexide in alkaline:
Measure mode . . . . . . . . . . EQU
dE [mV] . . . . . . . . . . . 0.5
dt [s] . . . . . . . .
t(min) [s] . . . . . .
.
.
.
.
.
.
.
.
1.0
3.0
Cd 2+ + Murexide - = Cu-Murexid +
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 50.0
Maximum volume [mL] . . . . . . . 20.0 • By titration with EDTA, Murexide is diplaced by
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 EDTA and forms a complex with Cd ions in an
Evaluation procedure . . . . . . Asymmetric
Rinse alkaline, neutral or weakly acid medium:
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Calculation
Result name . . . . . . . . . . . . Cadmium
Cd 2+ + H2-EDTA2- = Cd-EDTA2- + 2 H+
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C1=M/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . .
Rel. standard deviation srel
. . . . Yes
. . . . Yes Disposal
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Special waste
Application note:
Determination of Cd in a Cd-Ag alloy
Sample: 1.5 g Cd-Ag Alloy
Preparation: Add 20 mL HNO3 , boil to dissolve , cool
to room temperature, fill up to 100 mL with deionized
E-V curve
water. To aliquots of 5 mL add 10 mL buffer ph 4.5
solution and 5 drops HgEDTA
Indication: HgDM141, HgEDTA
Titrant: EDTA, c(EDTA)=0.1 mol/L
Titration parameter: INC (0.1 mL), EQU (0.5 mV/2 s)
Calculation: Q*C/m; C = M/(10*z), M = 112.40
Literature: DL40 application note 1986, Appl. Data-
base 40.8603
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Authors: Application Laboratory MT-Germany
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 47/100
METTLER TOLEDO
SHORT-FORM METHOD
Title vd03 Chromium (VI) in Cr-bath 23-Nov-1989 12:04
Sample 1 ST20A M=99.99, z=3
Stir 60 % 10 s
Titration Na2S2O3 DM140-SC EQP DYN EQU
Calculation R=Q*C/U C=M/z g/L
Rinse H2O 10.0 mL
Statistics R1
Record Printer
RESULTS
STATISTICS
Number results R1 n = 8
Mean value x = 150.24 g/L CrO3
Standard deviation s = 0.565 g/L CrO3
Rel. standard deviation srel = 0.376 %
Page 48/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method vd03 Chromium (VI) in Cr-bath Sample preparation
Version 23-Nov-1989 12:04
1) 1 mL chromium bath is diluted with deionized
Title water to 10 mL. 1 mL aliquot corresponds to 0.1
Method ID . . . . . . . . . . . . . vd03
Title . . . . . . . . . . . . . . . Chromium (VI) in Cr-bath mL original sample.
Date/time . . . . . . . . . . . . . 23-Nov-1989 12:04
Sample 2) 1 mL aliquot is diluted with 20 mL deion. water.
Number samples . . . . . . . . . . . 8
Titration stand . . . . . . . . . . ST20 3) 10 mL sulfuric acid 1:1 are added.
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1 4) Add 1.5 g potassium iodide (KI) and cover the bea-
Molar mass M . . . . . . . . . . . . 99.99 kers to avoid loss of iodine.
Equivalent number z . . . . . . . . 3
Stir
Speed [%] . . . . . . . . . . . . . 60
5) The sample solution is kept in the dark during 5-10
Time [s] . . . . . . . . . .
Titration
. . . . 10 minutes.
Titrant . . . . . . . . . . . . . . Na2S2O3
Concentration [mol/L] . . . . . . . 0.1 6) During this time, Cr(VI) is reduced by excess io-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DM140-SC
mV
dide (I-) to Cr(III):
Titration mode . . . . . . .
Predispensing . . . . .
.
.
.
.
.
.
.
.
EP
mL 2 Cr6+ + 6 I - → 2 Cr3+ + 3 I2 (z = 3)
Volume [mL] . . . . . . . . . 2.0
Titrant addition . . . . . . . . DYN The amount of iodine I2 formed is proportional to
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V [mL] . . . . . . . . Absolute the Cr(VI) content.
∆V(min) [mL] . . . . . . . 0.02
∆V(max) [mL] . . . . . . . 0.2 Titration of iodine
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 The formed I2 is then titrated with Na2S2O3:
∆t [s] . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 300.0 2 S2O32- + I2 → S4O62- + 2 I-
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard • Stir moderately. Vigorous stirring causes loss of I2
Calculation
Result name . . . . . . . . . . . . CrO3
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=Q*C/U
C=M/z
Table of measured values:
Result unit . . . . . . . . . . . . g/L
Volume Increment Signal Change 1st deriv. Time
Decimal places . . . . . . . . . . . 2
mL mL mV mV mV/mL min:s
Rinse
Auxiliary reagent . . . . . . . . . H2O
E1 0.000 298.6 0:03
Volume [mL] . . . . . . . . . . . . 10.0
1.143 1.143 296.6 -2.0 -1.8 0:09
Statistics
1.714 0.571 295.1 -1.5 -2.5 0:14
Ri (i=index) . . . . . . . . . . . . R1
E2 2.000 0.286 294.1 -1.0 -3.6 0:19
Standard deviation s . . . . . . . . Yes
2.200 0.200 293.3 -0.8 -4.2 0:23
Rel. standard deviation srel . . . . Yes
2.400 0.200 292.4 -0.8 -4.1 0:28
Record
2.600 0.200 291.4 -1.0 -5.2 0:35
Short-form method . . . . . . . . . Yes
2.800 0.200 290.2 -1.2 -6.2 0:40
Results last sample . . . . . . . . Yes
3.000 0.200 288.7 -1.4 -7.1 0:45
All results . . . . . . . . . . . . Yes
3.200 0.200 287.3 -1.5 -7.3 0:50
Table of measured values . . . . . . Yes
3.400 0.200 285.2 -2.1 -10.5 0:54
E - V curve . . . . . . . . . . . . Yes
3.600 0.200 282.8 -2.4 -12.0 0:59
3.800 0.200 279.7 -3.1 -15.5 1:03
4.000 0.200 275.6 -4.1 -20.3 1:08
4.200 0.200 268.8 -6.8 -34.2 1:12
4.367 0.167 257.4 -11.4 -68.0 1.18
Application note: 4.446
4.474
0.079
0.028
243.5
227.5
-13.9
-15.9
-176.5
-569.5
1.22
1:29
EQP1 4.494 0.020 190.7 -36.8 -1840.2 1:43
Cr(VI) in etching solutions 4.514 0.020 168.6 -22.2 -1108.1 1:53
4.535 0.021 160.8 -7.8 -371.3 2:01
Disposal
Special waste
Other titrators
DL50 Graphix, DL53/DL55, DL77. Author: Joop van den Ouweland, Mettler-Toledo NL
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 49/100
METTLER TOLEDO
Results:
Cr bath (g/L)
n = 2
x 4.2782
srel -- DL40 Appl. no. 308
Page 50/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40003 Cr(III) as Cr2O3
Version 16/01/2001 10:10
Title
Method ID . . . . . . . . . . . . . 40003
• The method was developed on the DL40 titrator
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Cr(III) as Cr2O3
. . . 16/01/2001 10:10
(see DL40 applications No. 308) and has been
Sample
Sample ID . . . . . . . . . . . . . Cr2O3
adapted for the DL5x- and DL7x-titrators.
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
5.0
• The Cr(III) content is expressed as Cr2O3 and is
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
152
3
detemined by back titration after addition of ex-
Titration stand . . . . . . .
Pump . . . . . . . . . . .
.
.
.
.
.
.
ST20A
No
cess cerium sulphate solution.
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O
Volume . . . . . . . .
Conditioning . . . . . . .
.
.
.
.
.
.
10.0
No
Sample preparation
Temperature sensor . . . . . .
Stir
. . . Manual
1) Add 10 mL nitric acid 1:1 to 5 mL chromium bath
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
. . . 50
. . . 10
in a glass beaker.
EQP titration
Titrant/Sensor 2) 50 mL acid cerium sulphate solution c(1/2
Titrant . . . . . . . . . . . . . 1/2 NaNO2
Concentration [mol/L] . . . . . . 0.2 Ce(SO4)2 = 0.05 mol/L) are added by using the dis-
Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . mV pensing function of the titrator. This corresponds to
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.0 2.5 mmol/L equivalent Ce(IV)
Wait time [s] . . . . . . . . . . 0
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.1 3) The sample solution is heated during 5 minutes at
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
Equilibrium controlled
0.5
50°C. During this time, Cr(III) is oxidized by ex-
∆t [s] . . . . . . . . . . . . . 1.0 cess Ce (IV) to Cr(VI):
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0
Recognition 3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+ (z = 3)
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No whereas Ce(IV) is reduced to Ce(III):
Tendency . . . . . . . . . . . . Negative
Termination
at maximum volume [mL] . . . . . 20.0 Ce4+ → Ce3+ + e-
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . .
comb. termination criteria
.
.
.
.
.
.
1
No
Procedure
Evaluation
Procedure . . . . . . . . . . . . Standard 1) A Ce(IV)-blank is determined using a similar meth-
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No od as for the determination of Cr(III). The blank
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 value is stored as auxiliary value H2 (mmol).
Calculation
Formula . . . . . . . . . . . . . . R=(H2-Q)*C/m 2) Cr(III) is then determined by a back-titration of ex-
Constant . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 4 cess Ce(IV) using sodium nitrite as a titrant:
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Cr2O3
Results:
Theoretical
content (g) 0.3067 0.232
Reactions
1) 1st FAS titration:
1.1 6 Fe2+ + Cr2O72- + 14 H+ → Fe3+ + 2 Cr3+ + 7 H2O
where
Cr2O72- + 14 H+ + 6 e- = 2 Cr3+ + 7 H2O (z = 6)
2) V3+ to V5+:
5V3+ + 2MnO4- + 16Η+ = 5V5+ + 2Mn2+ + 8Η2O
3) 2nd FAS titration: see 1.2
Page 52/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 25001 Cr/V
Version 16/01/2001 15:30
• The method was developed on the DL25 titrator
Title
Method ID . . . . . . . . . . . . . 25001
(see DL25 application no. 21) and has been adapt-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Cr/V
. . . 16/01/2001 15:30
ed for the DL5x- and DL7x-titrators.
Sample
Sample ID . . . . . . . . . . . . . K2Cr2O7/V2O5
• The sample is dissolved in sulphuric acid. It oxi-
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
25.0
didized with KMnO4 to ensure that chromium and
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
294.26
6
vanadium are present in their highest oxidation
Titration stand . . . . . . . . . . Stand 1 state. The first titration with FAS gives the sum of
Temperature sensor . . . . . . . . . Manual
Stir Cr and V in mmol. Iron (Fe(II)) reduces Cr(VI) to
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 Cr(III), while vanadium(V) is reduced to V(III).
EQP titration
Titrant/Sensor In a second step , V(III) is again oxidized by KMnO4
Titrant . . . . . . . . . . . . . FAS
Concentration [mol/L] . . . . . . 0.1 to V5+ and titrated with FAS. The difference be-
Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . mV tween the first and the second FAS titration accounts
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.0 for the chromium content.
Wait time [s] . . . . . . . . . . 15
Titrant addition . . . . . . . . . . Dynamic
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
.
.
.
.
.
.
4.0
0.1 Sample preparation
∆V(min) . . . . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.2
Equilibrium controlled
1) 0.5 g of sample are heated in 30 mL 10%
∆E [mV] . . . . . . . . . . . . . 0.5 sulphuric acid until complete dissolution.
∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
2) In a 250 mL flask dilute with deionized water.
Recognition 3) Take 25 mL aliquots and add KMnO4 solution
Threshold . . . . . . . . . . . . 200
Steepest jump only . . . . . . . No dropwise (KMnO4: 5g/100mL).
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Negative 4) Add 5 mL conc. HCl to eliminate excess
Termination
at maximum volume [mL] . . . . . 20.0 KMnO4 present in the solution.
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No 5) Heat until violet permanganate colour disap-
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 pears, and cool to room temperature.
comb. termination criteria . . . No
Evaluation 6) 1st titration with FAS (V2O5 + K2Cr2O7).
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No 7) Add again KMnO4 until violet is persistent.
Potential 2 . . . . . . . .
Stop for reevaluation . . .
.
.
.
.
.
.
No
Yes
8) Excess KMnO4 is eliminated by adding KNO2
Calculation
Condition . . . . . . . . . . neq=0 solution dropwise (KNO2 = 1g/100 mL).
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R=Q 9) Add 0.5 g urea to eliminate excess KNO2.
Decimal places . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
.
.
5
mmol
10) 2nd titration with FAS (V2O5).
Result name . . . . . . . . . . . . K2Cr2O7/V2O5 11) The difference between first and second result
Statistics . . . . . . . . . . . . . Yes
Calculation gives the chromium content.
Formula . . . . . . . . . . . . . . R2=VEQ
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Titrant cons.
Chemicals
Statistics . . . . . . . . . . . . . Yes
Calculation • Fe(NH4)2(SO4)2 • 6H2O (FAS):
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . mL flask with 10% sulphuric acid and fill to the
Statistics . . . . . . . . . . . . . No
Report mark with deionized water.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes Literature
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • DL25 application no. 21, in DL25 Application
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
.
.
.
.
.
.
No
No
Brochure "Chemicals", ME-51724629 (1994).
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
.
.
.
.
.
.
No
No
• Application no. M548 and M544, in Application
∆V/∆t - t curve . . . . . . . . . . No brochure 18, "Standardization of Titrants", 2000.
• "Metallurgische Analysen", József Mika,
Budapest
Disposal • "Handbuch für das Eisenhüttenlaboratorium", 2.
Special waste Band, Chemikerausschuss des Vereins
Deutscher Eisenhüttenleute.
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77. Author: Maria José Schmid
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 53/100
METTLER TOLEDO
Results:
ALL RESULTS
1 CrHe128/11 0.2 mL
R1 = 320.31 g/L Chroomzuur
2 CrHe128/11 0.2 mL
R1 = 320.55 g/L Chroomzuur
3 CrHe128/11 0.2 mL
R1 = 320.10 g/L Chroomzuur
STATISTICS
Number results R1 n = 3
Mean value x = 320.32 g/L Chroomzuur
Standard deviation s = 0.22772 g/L Chroomzuur
Rel. standard deviation srel = 0.071 %
Page 54/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 02 Chroom(VI)-bep in Cr-baden
Version 03-11-2000 10:58
Disposal
Special waste
Other titrators
DL53, DL58, DL70ES, DL77. Author: F. Saes, MT-NL/ W. Jongen
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 55/100
METTLER TOLEDO
Results:
CN- n Comments
Page 56/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 25003 Free CN- in Cu bath
Version 17-01-2001 10:50 • The cyanid content determination in e.g. brass elec-
Title
Method ID . . . . . . . . . . . . . 25003
troplating bath is very important to achieve opti-
. . . Free CN- in Cu bath
Title . . . . . . . . . .
Date/time . . . . . . . . . . . . . 17-01-2001 10:50
mum plating efficiency.
Sample
Sample ID . . . . . . . . . . . . . Cu bath • The method was developed on the DL25 titrator
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . . . . . . 1.0 and has been adapted for the DL5x-/DL7x-titrators.
Molar mass M . . . . . . . . . . . . 26.01
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . .
Temperature sensor . . . . . .
.
.
.
.
.
.
Stand 1
Manual Sample preparation
Stir
Speed [%] . . . . . . . . . . . . . 50
1) 10 mL copper bath are diluted to 100 mL with
Time [s] . . . . . . . . . . .
EQP titration
. . . 10 deionized water.
Titrant/Sensor
Titrant . . . . . . . . . . . . . AgNO3
2) 1 mL aliquot is poured in the titration beaker.
Concentration [mol/L] . . . . . . 0.1 3) Add 5 mL 10% potassium iodide solution (KI).
Sensor . . . . . . . . . . . . . DP550
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
.
.
.
.
.
.
mV
to volume
4) 40 mL deionized water is added to the sample.
Volume [mL] . . . . . . . . . . . 1.5
Wait time [s] . . . . . . . . . . 20
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
.
.
.
.
.
.
Dynamic
4.0
Reaction
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
.
.
.
.
.
.
0.02
0.2
• A soluble complex Ag(CN)2 - is first formed by
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
Equilibrium controlled
0.5
the reaction between silver and cyanide ion:
∆t [s] . . . . . . . . . . . . . 1.0 Ag+ + 2 CN- = Ag(CN)2 -
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0 As long as free cyanide is still present, the solu-
Threshold . . . . . . . . . . . . 200 tion remains clear, but the first excess of silver
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No causes formation of a white solid that mark the
Tendency . . . . . . . . . . . . Negative
Termination endpoint:
at maximum volume [mL] . . . . . 20.0
at potential . . . . . . . . . . No Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes • To obtain a accurate determination of the
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No endpoint, potassium iodide is used as an indica-
Evaluation
Procedure . . . . . . . . . . . . Standard tor.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No During titration, any silver iodide which would
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 tend to form will be kept in solution by the excess
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m of cyanide ion always present until the equiva-
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
2
lence point is reached:
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
g/L
Sample content
AgI + 2 CN- = [Ag(CN)2] - + I-
Statistics . . . . . . . . . .
Calculation
. . . Yes
• After the equivalence point, the formation of yel-
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=R1*10
low silver iodide will lead to a turbidity increase
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L which indicates the end point.
Result name . . . . . . . . . . . . Bath content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=Q*C3 Chemicals
Constant . . . . . . . . . . . . . . C3=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg • 10% Potassium iodide, KI: 50 g KI and 50 g
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
CN in sample
No
NaOH are dissolved in deionized water, and di-
Report
Output . . . . . . . . . . . . . . . Printer
luted to 500 mL in a volumetric flask.
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . .
Sample data . . . . . . . . .
.
.
.
.
.
.
Yes
No
Literature
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • Application note, DL25 Application Brochure
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No "Petroleum and electroplating", ME-51724627.
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No • Vogel's textbook of quantitative inorganic analy-
∆V/∆t - t curve . . . . . . . . . . No
sis, 4th edition, Longman Group Limited , 1978.
• D.A. Skoog, D.M. West, "Fundamentals of Ana-
Disposal lytical Chemistry", Holt, Rinehart, and Winston,
Cyanide waste 1969.
• Application no. M525 in Application bro-
chure18, "Standardization of Titrants", 2000.
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77. Author: R. Böhlen, MT Switzerland
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 57/100
METTLER TOLEDO
Results:
CN- n Comments
as NaCN, M=49
Page 58/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40004 Free CN- in Zn bath
Version 18-01-2001 10:13
• The method was developed on the DL40 titrator
Title
Method ID . . . . . . . . . . . . . 40004
and has been adapted for the DL5x- and DL7x-ti-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Free CN- in Zn bath
. . . 18-01-2001 10:13
trators.
Sample
Sample ID . . . . . . . . . . . . . Zn bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
1.0
Sample preparation
Molar mass M . . . . . . . . . . . . 26.01 1) 1 mL zinc bath are diluted in a titration beaker
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . . . . . Stand 1 by adding 40 mL deionized water.
Temperature sensor . . . . . . . . . Manual
Stir 2) 5 mL 20% NaOH solution are added.
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . AgNO3
Reaction
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DM141
• The following equation describes the interde-
Unit of meas. . . . . . . . . . . mV pendence of the different ions in a zinc bath:
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 1.0
Wait time [s] . . . . . . . . . . 10
Titrant addition . . . . . . . . . . Dynamic Na2Zn(CN)4 + 4NaOH = Na2ZnO2 + 4NaCN + 2H2O
∆E(set) [mV] . . . . . . . . . . 8.0
∆V(min) [mL] . . . . . . . . . . 0.02
∆V(max) [mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled If excess sodium hydroxde is added, then all
∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 1.0 cyanide is set free, and can be precipitated by
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0 silver ions Ag+ added during titration:
Recognition
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
Ag+ + 2 CN- = [Ag(CN)2] -
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
15.0
No
Note that silver forms i a first step the soluble
at slope . . . . . . . . . . . . No complex Ag(CN)2- .
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard
• The indication with the DM141 combined silver
Potential 1 . . . . . . . . . . . No electrode is superior to the traditional turbidi-
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes metric indication with potassium iodide.
Condition . . . . . . . . . . neq=0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z • The Zn content analysis is described in appl.
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L M191
Result name . . . . . . . . . . . . Bath content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=Q*C2
C2=M*1000/z
Literature
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mg
CN in sample
• DL40 application no. 168
Statistics . . . . . . . . . .
Calculation
. . . Yes • Vogel's textbook of quantitative inorganic analy-
Formula . . . . . . . . . . . . . . sis, 4th edition, Longman Group Limited , 1978.
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 • Application no. M525 in Application bro-
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . chure18, "Standardization of Titrants", 2000.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No E-V curve (DL40 application):
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Cyanide waste
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: U. Büchi / P. Schauwecker
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 59/100
METTLER TOLEDO
Results:
Zn2+ n Comments
Page 60/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40005 Zn in Zn bath
Version 18-01-2001 10:30
• The method was developed on the DL40 titrator
Title
Method ID . . . . . . . . . . . . . 40005
and has been adapted for the DL5x- and DL7x-ti-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Zn in Zn bath
. . . 18-01-2001 10:30
trators.
Sample
Sample ID . . . . . . . . . . . . . Zn bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
1.0
• Adjust the DP 550 at 1000 mV in deionised water
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
65.37
1
before starting titration (100% transmission).
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual
Dispense
Titrant . . . . . . . . . . . . . . EDTA
Sample preparation
Concentration [mol/L] . . . . . . . 0.1
Volume [mL] . . . . . . . . . . . . 6.0
Stir
Speed [%] . . . . . . . . . . . . . 50
1) 1 mL zinc bath are diluted in a titration beaker
Time [s] . . . . . . . . . . .
EQP titration
. . . 20 by adding 50 mL deionized water.
Titrant/Sensor 2) 5 mL buffer solution pH 10 are added
Titrant . . . . . . . . . . . . . ZnSO4
Concentration [mol/L] . . . . . . 0.1 3) 5 mL 37-40% formaldehyde solution are added.
Sensor . . . . . . . . . . . . . DP550
Unit of meas. . . . . . . . . . . mV 4) 0.5 mL indicator solution are added before
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.5 titration.
Wait time [s] . . . . . . . . . . 10
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.02
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
Equilibrium controlled
0.2
Reaction
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0 • Zn is determined by back titration after addition
Threshold . . . . . . . . . . . . 1000 of an excess of EDTA (6 mL).
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No 1. Zn(II) ions form complexes with EDTA:
Tendency . . . . . . . . . . . . Negative
Termination
at maximum volume [mL] . . . . . 10.0
at potential . . . . . . . . . . No Zn 2+ + H2-EDTA2- = Zn-EDTA2- + 2 H+
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No 2. EDTA excess is titrated with 0.1 mol/L zinc
Evaluation
Procedure . . . . . . . . . . . . Standard sulphate solution according to the above reaction.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 3. The colour change of Erio T in alkaline medium
Calculation
Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m
will be from blue to red when EDTA is titrated
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
2
with Zn(II).
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Bath content
Statistics . . . . . . . . . .
Calculation
. . . Yes
Chemicals
Formula . . . . . . . . . . . . . . R2=R1*C2
Constant . . . . . . . . . . . . . . C2=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg • Buffer solution pH 10:
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Zn in sample
Yes
70 g ammonium chloride, NH4Cl, and 570 mL
Calculation
Formula . . . . . . . . . . . . . .
ammonium hydroxide, NH4OH, are dissolved in
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 0
1000 mL volumetric flask. Diluto to the mark
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
with deionized water.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No Literature
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes • DL40 application no. 175
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
.
.
.
.
.
.
No
Yes
• Applications no. M528 and 538 in Application
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
.
.
.
.
.
.
Yes
No
brochure18, "Standardization of Titrants", 2000.
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Zinc is precipitated as zinc hydroxide with NaOH or
Ca(OH)2 and then filtrated (precipitate: special waste).
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: U. Büchi / P. Schauwecker
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 61/100
METTLER TOLEDO
Results:
Au3+ n Comments
Page 62/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40005 Au(III)
Version 18-01-2001 16:30 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . . . . . 40005
Title . . . . . . . . . . . . . Zn in Zn bath trators.
Date/time . . . . . . . . . . . . . 18-01-2001 16:30
Sample
Sample ID . . . . . . . . . . . . . Au-solution
Entry type . . . . . . . . . . . . . Fixed volume Sample preparation
Volume [mL] . . . . . . . . . . . 5.0
Molar mass M . . . . . . . . . . . . 196.97 1) 5mL standard solution are diluted in a titration
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 beaker by adding 50 mL deionized water.
Temperature sensor . . . . . . . . . Manual
Stir 2) Adjust to pH 3-5 by carefully adding 1 mol/L
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 nitric acid (or more concentrated, if necessary).
EQP titration
Titrant/Sensor CAUTION:
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
AgNO3
0.1
If the pH is lowered below pH 3, then HCN is
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
DM141
mV
formed, which is extremely toxic! Therefore
Predispensing . . . . . . . .
Titrant addition . . . . . . .
.
.
.
.
.
.
No
Dynamic
work in a fume hood.
∆E(set) [mV] . . . . . . . . . . 8.0
∆V(min) [mL] . . . . . . . . . . 0.02
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.2
Equilibrium controlled
Reaction
∆E [mV] . . . . . . . . . . . . . 0.5 • Gold is precipitated as AgAu(CN)2 during titra-
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
tion with silver nitrate:
Recognition
Threshold . . . . . . . . . . . . 800
Steepest jump only . . . . . . . No Ag + + Au(CN)2- = AgAu(CN)2
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
10.0
No
Nitric acid is added to increase the steepness of
at slope . . . . . . . . . . . . No the potential jump at the equivalence point.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation • If the standard solution should contain chloride,
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No then the latter can be determined by continuing
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes the analysis until a second equivalence point is
Condition . . . . . . . . . . neq=0
Calculation found. This is due to the precipitation of silver
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z chloride in the sample solution.
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Au content
Yes
• Gold electroplating baths contain free cyanide.
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
Interference from free cyanide can be avoided by
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 3
adjusting the pH to 5-6 using 30-40% formalde-
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Consumption
hyde solution. After a waiting time of 15-20 min-
Statistics . . . . . . . . . .
Calculation
. . . Yes utes, the titration can be started.
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
.
.
.
.
.
.
No
No Literature
∆V/∆t - t curve . . . . . . . . . . No
• DL40 application no. 8121, 1982.
Results:
Page 64/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Introduction Chemistry and Calculations
To determine pure gold or its content in alloys we have 1. Gold (Au) is oxidized to the Au3+ ion by aqua regia.
chosen the precipitation method with hydroquinone. 2. Au3+ is reduced by an excess of hydroquinone:
Most of the associated metals do not interfere with the Au precipitates and quinone is formed
determination. As the precipitation of gold is too slow to
OH O
execute a direct titration with hydroquinone, an excess
of hydroquinone is added to the dissolved gold. The pH ~ 1
excess is titrated back with cerium sulfate. Three individual 2 Au3+ + 3 = 2 Au + 6H+ + 3
methods are necessary for the gold determination: 6e -
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 65/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 4
Mean value x = 0.98199 Factor
Standard deviation s = 0.000611 Factor
Rel. standard deviation srel = 0.062 %
Outlier test: no outliers!
AUXILIARY VALUE
New value H2 = 0.981989 Factor
Page 66/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method "cer" Remarks
Method cer Factor Ce(SO4)2/C6H4(OH)2
Version 02-April-1993 13:35 • The cerium sulfate solution is unstable because a
Title precipitation occurs. We recommend to prepare a
Method ID . . . . . . . . . . . . . cer
Title . . . . . . . . . . . . . . . Factor Ce(SO4)2/C6H4(OH)2 new solution every 2 days.
Date/time . . . . . . . . . . . . . 02-April-1993 13:35
Sample
Number samples . . . . . . . . . . . 4
• The hydroquinone solution is stable but we
Titration stand . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Stand 1
Fixed volume U
recommend to prepare a new solution every 10
Volume [mL] . . . . . . . .
ID1 . . . . . . . . . . . . .
.
.
.
.
.
.
1.5 mL
C6H6O2
days.
Molar mass M . . . . . . . . . . . . 110.11
Equivalent number z . . . . . . . . 2
Temperature sensor . . . . . .
Pump
. . . Manual
Calculation
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
Volume [mL] . . . . . . . . . . . . 40.0 • Fixed volume U of hydroquinone =
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2 dispensed volume VDISP = 1.5 mL
Concentration . . . . . . . . . . . 0.05
Volume [mL] . . . . . . . . . . . . 1.5
Stir
Speed [%] . . . . . . . . . . . . . 50 VDISP * c(1/2 C6H6O2)
Time [s] . . . . . . . . . . .
Titration
. . . 10
fce/hy =
Titrant . . . . . . . . . . .
Concentration [mol/L] . . . .
.
.
.
.
.
.
Ce(SO4)2
0.01
VEQ * c(Ce(SO4)2)
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predespensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 6.3 • If the mean value ❘ of fce/hy is less than 0.9 or greater
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0 than 1.1, the INSTRUCTION function is displayed.
Limits ∆V . . . . . . . . . . Absolute
∆V (min) [mL] . . . . . . . 0.01
∆V (max) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU • The mean value ❘ of fce/hy is stored as auxiliary value
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 2.0 H2. It is used to calculate the titer of cerium sulfate
t(min) [s] . . . . . . .
t(max) [s] . . . . . . .
.
.
.
.
.
.
3.0
30.0 versus gold (see method "hydr").
Threshold . . . . . . . . . . . . 2000.0
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs .
n = . . . . . . . . . .
.
.
.
.
.
.
Yes
1 Table of measured values
Evaluation procedure . . . . . . Standard
Calculation Volume Increment Signal Change 1st deriv. Time
Result name . . . . . . . . . . . . Factor mL mL mV mV mV/mL min:s
Formula . . . . . . . . . . . . . . R=VDISP*0.05/(VEQ*c)
ET1 0.0000 432.8 0:30
Constant . . . . . . . . . . . . . .
3.6000 3.6000 455.0 22.2 6.2 0:57
Result unit . . . . . . . . . . . .
5.4000 1.8000 468.6 13.6 7.5 1:16
Decimal places . . . . . . . . . . . 5 ET2 6.3000 0.9000 479.6 11.1 12.3 1:31
Statistics 6.5000 0.2000 482.2 3.1 15.4 1:40
Ri (i=index) . . . . . . . . . . . . R1 6.7000 0.2000 486.7 4.0 20.2 1:49
Standard deviation s . . . . . . . . Yes 6.9000 0.2000 491.3 4.6 23.1 2:04
Rel. standard deviation srel . . . . Yes 7.1000 0.2000 498.1 6.8 33.9 2:19
Outlier test . . . . . . . . . . . . Yes 7.2780 0.1780 507.0 8.9 49.9 2:37
Instruction 7.3990 0.1210 517.1 10.1 83.3 2:54
At least one solution is bad! 7.4670 0.0680 525.1 8.1 118.4 3:10
Please renew! 7.5190 0.0520 534.6 9.5 181.7 3:27
Condition . . . . . . . . . . . . . Yes 7.5510 0.0320 542.5 7.9 247.2 3:44
Condition . . . . . . . . . . . . (x<0.9)?(x>1.1) 7.5760 0.0250 551.7 9.2 366.8 4:07
Auxiliary value 7.5920 0.0160 561.0 9.4 586.2 4:24
ID text . . . . . . . . . . . . . . Factor 7.6020 0.0100 567.9 6.9 686.0 4:41
Formula . . . . . . . . . . . . . . H2=x 7.6120 0.0100 578.7 10.9 1085.0 4:58
Record 7.6220 0.0100 595.1 16.3 1630.9 5:18
Output unit . . . . . . . . . . . . Printer EQP1 7.6320 0.0100 640.9 45.8 4585.0 5:39
All results . . . . . . . . . . . . Yes 7.6420 0.0100 681.5 40.6 4059.8 5:53
Table of values . . . . . . . . . . Yes 7.6520 0.0100 708.5 27.0 2702.0 6:13
E - V curve . . . . . . . . . . . . Yes
E-V curve
Results:
Page 68/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method hydr
Version
Titer of C6H6O2, Ce(SO4)2
06-April-1993 13:39
Sample Preparation
Title
Method ID . . . . . . . . . . . . . hydr A careful sample preparation is mandatory for reprodu-
Title . . . . . . . . . . .
Date/time . . . . . . . . .
. . . . Titer of C6H6O2, Ce(SO4)2
. . . . 06-April-1993 13:39
cible results.
Sample – Weigh in a gold sample of approx. 0.025 g.
Number samples . . . . . . . . . . . 4
Titration stand . . . . . . . . . . Stand 1 – Clean it with ethanol and let it dry - use tweezers.
Entry type . . . . . . . . .
Lower limit [g] . . . . .
.
.
.
.
.
.
.
.
Weight m
0.023
– Weigh in this sample with a precision of 0.001 mg
Upper limit [g] . . . . . . . . . 0.026 and put it in the glass beaker.
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . . . . . . 196.967 – Add 5 mL conc. HCl and 1.5 mL conc. HNO3 (fume
Equivalent number z . . . . . . . . 3
Temperature sensor . . . . . . . . . Manual hood). Never use prepared aqua regia, it is unstable!
Pump
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
– To dissolve the gold place the beaker on a heating
Volume [mL] . . . . . . . . . . . . 40.0 plate (110 to 130 °C).
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2 The dissolution time can be reduced by using an
Concentration . . . . . . .
Volume [mL] . . . . . . . .
. . . . 0.05
. . . . 1.4*H2+304.6*m
ultra-sonic bath (room temperature).
Stir – Evaporate to almost dryness (color changes from
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 180 yellow to orange), but never evaporate to complete
Calculation
Result name . . . . . . . . . . . . dryness! This would cause the reduction of gold and
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=VDISP*5/H2-C
C=m*1523*H2
give false results!
Result unit . . . . . . . . . . . . mL – Rinse the beaker walls with 5 mL conc. HCl and eva-
Decimal places . . . . . . . . . . . 3
Titration porate again to eliminate the nitrous compounds.
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
Ce(SO4)2
0.01
– Repeat this procedure until no yellow fumes are
Sensor . . . . . . . . . . . . . . . DM140-SC formed anymore.
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP – Let the sample cool to room temperature, then titrate.
Predespensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 0.9*R
Titrant addition . . . .
∆E(set) [mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0
Table of measured values
Limits ∆V . . . . . . . . . . Absolute Volume Increment Signal Change 1st deriv. Time
∆V (min) [mL] . . . . . . . 0.01 mL mL mV mV mV/mL min:s
∆V (max) [mL] . . . . . . . 0.2
ET1 0.0000 449.7 0:03
Measure mode . . . . . . . . . . EQU 2.5020 2.5020 457.5 7.8 3.1 0:13
∆E [mV] . . . . . . . . . . . 0.5 3.7530 1.2510 462.6 5.0 4.0 0:21
∆t [s] . . . . . . . . . . . . 2.0 ET2 4.3800 0.6270 465.8 3.3 5.2 0:27
t(min) [s] . . . . . . . . . . 3.0 4.5800 0.2000 467.1 1.3 6.3 0:32
t(max) [s] . . . . . . . . . . 30.0 4.7800 0.2000 468.4 1.3 6.7 0:37
4.9800 0.2000 469.8 1.4 7.0 0:42
Threshold . . . . . . . . . . . . 1000.0
5.1800 0.2000 471.4 1.6 8.1 0:47
EQP range . . . . . . . . . . . . Yes 5.3800 0.2000 473.1 1.7 8.4 0:53
Limit A . . . . . . . . . . . 500 5.5800 0.2000 475.2 2.1 10.5 0:58
Limit B . . . . . . . . . . . 800 5.7800 0.2000 477.4 2.2 10.9 1:04
Maximum volume [mL] . . . . . . . 10.0 5.9800 0.2000 480.1 2.7 13.7 1:09
Termination after n EQPs . . . . Yes 6.1800 0.2000 483.6 3.4 17.2 1:15
6.3800 0.2000 488.1 4.6 22.8 1:22
n = . . . . . . . . . . . . . 1
6.5800 0.2000 495.2 7.1 35.3 1:28
Evaluation procedure . . . . . . Standard 6.7460 0.1660 506.4 11.2 67.5 1:37
Calculation 6.8260 0.0800 520.1 13.7 171.5 1:46
Result name . . . . . . . . . . . . C6H6O2 6.8550 0.0290 530.0 9.9 340.3 1:54
Formula . . . . . . . . . . . . . . R2=VDISP*0.05 6.8700 0.0150 539.9 9.9 662.6 2:03
Constant . . . . . . . . . . . . . . 6.8800 0.0100 548.6 8.7 868.0 2:15
6.8900 0.0100 558.8 10.2 1022.0 2.30
Result unit . . . . . . . . . . . . mmol
6.9000 0.0100 571.0 12.3 1225.0 2:46
Decimal places . . . . . . . . . . . 5 6.9100 0.0100 589.5 18.4 1840.9 3:07
Calculation 6.9200 0.0100 625.8 36.3 3633.0 3:38
Result name . . . . . . . . . . . . Titer C6H6O2 EQP1 6.9300 0.0100 679.2 53.4 5340.8 4:08
Formula . . . . . . . . . . . . . . R3=C3/(R2-VEQ*c*H2) 6.9400 0.0100 703.3 23.1 2408.0 4:30
Constant . . . . . . . . . . . . . . C3=(m*1000*z)/M 6.9500 0.0100 712.1 8.8 882.0 4:40
Result unit . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 5
Statistics E-V curve
Ri (i=index) . . . . . . . . . . . . 3
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
Titer
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Concentration [mol/L] . . . . . . . 0.05
Formula t = . . . . . . . x
Titer
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Concentration [mol/L] . . . . . . . 0.01
Formula t = . . . . . . . x*H2
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Auxiliary value Disposal
ID text . . . . . . . . . . . . . . Titer of C6H6O2
Formula . . . . . . . . . . . . . . H3=x Special waste.
thy = z * m * 1000
1
M (VDISP * c( /2 C6H6O2) – VEQ * c(Ce(SO4)2) * fce/hy)
Page 70/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 71/100
METTLER TOLEDO
Sample: Various gold alloys with a known Instruments: - METTLER TOLEDO DL70ES/77
(±10%) gold content - METTLER balance AT261
0.02 - 0.08 g - Printer: HP Deskjet
RESULTS
STATISTICS
Number results R1 n = 4
Mean value x = 38.058 % purity
Standard deviation s = 0.041247 % purity
Rel. standard deviation srel = 0.108 %
Outlier test: no outliers!
STATISTICS
Number results R2 n = 4
Mean value x = 9.134 carat purity
Standard deviation s = 0.009899 carat purity
Rel. standard deviation srel = 0.108 %
Outlier test: no outliers!
AUXILIARY VALUE
New VALUE H4 = 0.375
Page 72/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method "gold" Remarks
Method gold Purity of gold samples • Before executing this method the carat or percent
Version 08-April-1993 8:48
value of the alloy has to be entered as auxiliary value
Title
Method ID . . . . . . . . . . . . . gold
H1. If the gold content is unknown, use the "test"
Title . . . . . . . . . . . . . . . Purity of gold samples method (see M180). Enter thy as H3.
Date/time . . . . . . . . . . . . . 08-April-1993 8:48
Sample • The gold concentration of the sample entered as
Number samples . . . . . . . . . . . 4
Titration stand . . . . . . . . . . Stand 1 carat or percent is automatically transformed into the
Entry type . . . . . . . . .
Lower limit [g] . . . . .
.
.
.
.
.
.
.
.
Weight m
0.02
fraction of gold and stored as H4 using the AUXILIARY
Upper limit [g] . . . . . . . . . 0.08 VALUE functions.
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . . . . . . 196.967
Equivalent number z . . . . . . . . 3 Sample Preparation
Temperature sensor . . . . . . . . . Manual
Auxiliary value
ID text . . . . . . . . . . . . . .
Proceed with the sample preparation as described in
Formula . . . . . . . . . . . . . . H4=H1/24 method "hydr". The following remarks are important:
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . H1<=24 • Press alloys as thin as possible using a rolling device
Auxiliary value
ID text . . . . . . . . . . . . . . so that the dissolution is easier.
Formula . . . . . . . . . . . . . . H4=H1/100
Condition . . . . . . . . . . . . . Yes • Use an ultrasonic bath especially for silver alloys, be-
Condition . . . . . . . . . . . . (H1>24)!(H1<=100)
Pump cause silver chloride does passivate the gold surface.
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
Volume [mL] . . . . . . . . . . . . 40.0 • Evaporate the aqua regia solution.
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2 • Add 5 mL conc. HCl to the beaker and put it in the
Concentration . . . . . . . . . . . 0.05
Volume [mL] . . . . . . . . . . . . 1.2*H2+304.6*m*H4/H3
ultrasonic bath for 5 minutes.
Stir
Speed [%] . . . . . . . . . . . . . 50 • Evaporate again.
Time [s] . . . . . . . . . . . . . . 180
Titration • If the alloy is not yet dissolved, repeat the procedure.
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Concentration [mol/L] . . . . . . . 0.01 • Never evaporate to complete dryness!
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . .
Predespensing 1 . . . . .
.
.
.
.
.
.
.
.
EQP
mL
Sample Weight (g)
Volume [mL] . . . . . . . . . 2.1
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0
Content (carat) lower limit upper limit
Limits ∆V . . . . . . . . . . Absolute
∆V (min) [mL] . . . . . . . 0.02
24 0.023 0.026
∆V (max) [mL] . . . . . . . 0.2 21 0.026 0.030
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 18 0.031 0.034
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 14 0.040 0.044
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 400.0 12 0.046 0.052
EQP range . . . . . . . . . . . . Yes
Limit A . . . . . . . . . . . 500 9 0.062 0.069
Limit B . . . . . . . . . . . 700
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 Dispensing of Hydroquinone
Evaluation procedure . . . . . . Standard
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
purity
R=100*(QDISP-Q)*C
• An excess of hydroquinone is dispensed depending
Constant . . . . . . . . . . . . . . C=M/(m*z*1000) on the sample size and the gold concentration.
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 3 • Furthermore, the dispensed volume (VDISP) is
Calculation
Result name . . . . . . . . . . . . purity
calculated for a consumption of 6 mL cerium sulfate
Formula . . . . . . . . . . . . . . R2=24*(QDISP-Q)*C2 during the back titration. VDISP is determined and
Constant . . . . . . . . . . . . . . C2=M/(m*z*1000)
Result unit . . . . . . . . . . . . carat dispensed by the DISPENSE function.
Decimal places . . . . . . . . . . . 3
Statistics
Ri (i=index) . . . . . . . . . . . . R1
VDISP =
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
= mL hydroquinone + mL hydroquinone back
Statistics reacted with gold titrated with Ce(SO4)2
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes z * m * Aux * 1000 6 mL * c(Ce(SO4)2) * fce/hy
Outlier test . . . . . . . . . . . . Yes = 1
+
Record M * c( /2 C6H6O2) * thy c(1/2 C6H6O2)
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
= 304.6 * m * H4/H3 + 1.2 * H2
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 73/100
Calculation of the result Reaction Time
• The complete reduction of gold with hydroquinone
takes about 3 minutes; thus the stirring time shall not
The gold content Au is:
be less than 180 s.
Disposal
Special waste.
Other titrators
DL70ES, DL77. Authors: MT Analytical, Application laboratory
Page 74/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
METTLER TOLEDO
Sample: Lead for batteries (PbO2: 8-30%) Instruments: METTLER TOLEDO DL53
0.5 - 1 g Matrix printer Epson LX800
with serial inteface 8148
Substance: Lead, Pb4+ as lead oxide, PbO2 AT261
M = 239.2, z = 2
Method: 40006
Preparation: 30% HNO3 , 15 mL
10% H2O2 , 5 mL Accessories: Glass titration beakers
Hot deioniezd water, 30 mL. ME-101446
PbO2 n Comments
Page 76/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40006 PbO2
Version 19-01-2001 17:32 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-
Method ID . . . . . . . . . . . . . 40006
Title . . . . . . . . . . . . . PbO2 titrators.
Date/time . . . . . . . . . . . . . 19-01-2001 17:32
Sample • The Pb(IV) content is expressed as PbO2 and is
Sample ID . . . . . . . . . . . . . Lead in batteries
Entry type . . . . . . . . . . . . . Weight detemined by back titration after addition of ex-
Lower limit [g] . . . . . . . . . 0.5
Upper limit [g] . . . . . . . . . 1.5 cess hydrogen peroxide solution.
Molar mass M . . . . . . . . . . . . 239.2
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Sample preparation
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
EQP titration 1) Dissolve the sample in a glass titration beaker by
Titrant/Sensor
Titrant . . . . . . . . . . . . . 1/5 KMnO4 adding 15 mL of 30% nitric acid HNO3. Stir the
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DM140 solution until all red traces are dissolved.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No 2) 5 mL 10% hydrogen peroxide solution are added
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
.
.
.
.
.
.
Dynamic
8.0
by using the dispensing function of the titrator.
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
.
.
.
.
.
.
0.02
0.2
Pb(IV) is reduced to Pb(II) by H2O2:
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 2.0
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
.
.
.
.
.
.
1.0
5.0
Pb4+ + H2O2 = Pb2+ + O2 + 2 H+ (z = 2)
t(max) [s] . . . . . . . . . . . 30.0
Recognition
Threshold . . . . . . . . . . . . 300 Pb4+ + 2 e- = Pb2+
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive
Termination 3) 30 mL hot deionized water are added and stir to
at maximum volume [mL] . . . . . 30.0
at potential . . . . . . . . . . No achieve complete solvation.
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard Procedure
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes 1) The exact concentration of the H2O2-solution is de-
Condition . . . . . . . . . . neq=0
Calculation termined by performing a blank titration using a
Formula . . . . . . . . . . . . . . R=(H4-Q)*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) similar method as for the sample determination. The
Decimal places . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
.
.
4
%
blank value is stored as auxiliary value H4 (mmol).
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Pb content
Yes
2) Pb(IV) is then determined by a back-titration of
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
excess H2O2 using potassium permanganate as a
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 3
titrant:
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption
Statistics . . . . . . . . . .
Calculation
. . . Yes 2MnO4 - + 5 Η2Ο2 + 6 H+ = 2Mn2+ + 5O2 + 8Η2O
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . (z =2)
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No
Literature
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No • DL40 application no. 305
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • Application no. M527 in Application bro-
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No chure18, "Standardization of Titrants", 2000.
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: MT Analytical, Application laboratory
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 77/100
METTLER TOLEDO
Results:
Pb2+ n Comments
Consumption: 1.7 mL
Rel. standard 0.34 %
deviation srel
Buffer pH 4.5:
Hexamethylene tetramine: 400 g
Hydrochloric acid:100 mL
Dilute with deion. water to 1 L
Page 78/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40007 Pb2+
Version 22-01-2001 10:47 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-
Method ID . . . . . . . . . . . . . 40007
Title . . . . . . . . . . . . . Pb2+ titrators.
Date/time . . . . . . . . . . . . . 22-01-2001 10:47
Sample • The Pb(II) content is detemined by complexomet-
Sample ID . . . . . . . . . . . . . Pb/Sn/Sb alloy
Entry type . . . . . . . . . . . . . Fixed volume ric titration with EDTA.
Volume [mL] . . . . . . . . . . . 10.0
Molar mass M . . . . . . . . . . . . 207.2
Equivalent number z . . . . . . . . 1
Titration stand . . . .
Pump . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
ST20A
No
Sample preparation
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O
Volume . . . . . . . . . . . 20.0 1) Dissolve 1-1.5 g of the finely pulverized alloy in a
Conditioning . . . . . . . . . . No
Temperature sensor . . . . . . . . . Manual 250 mL beaker.
Stir
Speed [%] . . . . . . . . . . . . . 50 2) Add 20 mL 1:1 HCl and heat
Time [s] . . . . . . . . . . . . . . 10
EQP titration 3) To the hot solution add 10 mL of 1.1 HNO3, heat
Titrant/Sensor
Titrant . . . . . . . . . . . . . EDTA until dissolution is complete.
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DP550 4) Add 20 mL of 4% KCl, 50 mL of 1.1 HCl, 50 mL
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No deion. water and 20 mL 20% tartaric acid solution.
Titrant addition . . . .
∆V [mL] . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
Incremental
0.05
5) Boil 2 minutes.
Measure mode . . . . . . . . . . . . Equilibrium controlled
6) Cool to room temperature.
∆E [mV] . . . . . . . . . . . . . 0.5 7) Add 5 drops of 0.2% aqueous solution of xylenol
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
orange and 30% hexamethylene tetramine until the
Recognition solution turns red (for this sample size you need
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . . . . . No about 35 mL).
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive 8) Dilute to 200 mL with 1:1 HCl.
Termination
at maximum volume [mL] . . . . . 5.0 9) Take aliquots of 10 mL.
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 Procedure
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard 1) This procedure is only suitable for the determina-
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No tion of Pb in Pb/Sn/Sb alloy. The alloy is dissolved
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 due to the formation in a strong acid medium of a
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m soluble chloro-plumbate complex.
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/(10*z)
2
2) The solution is diluted to volume using 1:1 HCl
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
%
Pb content
since no precipitate is formed at high concentra-
Statistics . . . . . . . . . .
Calculation
. . . Yes tion of HCl.
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=VEQ 3) Sn and Sb are masked by tartaric acid. Pb can be
Decimal places . . . . . . . . . . . 3 directly determined by titration with EDTA:
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . .
Pb2+ + H2-EDTA2- = Pb-EDTA2- + 2 H+
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 The colour change at the equivalence point turns
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . from red to yellow.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes Literature
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • DL40 application no. 406
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
.
.
.
.
.
.
No
No
• Application no. M528 in Application bro-
∆V/∆t - t curve . . . . . . . . . . No chure18, "Standardization of Titrants", 2000.
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: MT Analytical, Application laboratory
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 79/100
METTLER TOLEDO
RESULTS
STATISTICS
Number results R1 n = 8
Mean value x = 82.39 g/L NiSO4.6H2O
Standard deviation s = 0.225 g/L NiSO4.6H2O
Rel. standard deviation srel = 0.273 %
Page 80/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method vd01 Nickel in Galvanic Bath
Version 13-Sep-1991 15:22 • The Ni(II) content is detemined by complexomet-
Title ric titration with EDTA. Murexide is used as indi-
Method ID . . . . . . . . . . . . . vd01
Title . . . . . . . . . . . . . Nickel in Galvanic Bath
cator, and the colour change is monitored by a
Date/time . . . . . . . . .
Sample
. . . . 13-Sep-1991 15:22 DP550 phototrode.
Number samples . . . . . . . . . . 8
Titration stand . . . . . . . . . . ST20
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 0.5 Sample preparation
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
. 262.7
1) Add the mureide indicator to the sample
Equivalent number z . . . .
Pump
. . . . 1 2) The addition of water and buffer is performed au-
Auxiliary reagent . . . . . . . . . H2O tomatically by two peristaltic pumps.
Volume [mL] . . . . . . . . . . . . 10.0
Pump
Auxiliary reagent . . . . . . . . . Buffer 10
Volume [mL] . . . . . . . .
Stir
. . . . 10.0 Procedure
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 • Nickel ions forms a yellow complex with murex-
Titration
Titrant . . . . . . . . . . . . . . EDTA ide in alkaline solution:
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
.
.
.
.
.
.
.
.
DP550
As installed
Ni 2+ + Murexide - → Ni-Murexid+
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL Ni forms a more stable complex with EDTA:
Volume [mL] . . . . . . . . . 0.5
Titrant addition . . . .
∆E(set)[mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0 Ni-Murexid+ + EDTA 4- → Ni-EDTA2-+ Murexide-
Limits ∆V . . . . . . . . . . Absolute
∆V(min) . . . . . . . . . . 0.02 At the equivalence point, Ni(II) has been
∆V(max) . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . EQU complexed by EDTA and murexide is free in the
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 1.0 alkaline solution. There is a colour change from
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 yellow to blue-violet.
Threshold . . . . . . . . . . . 10.0
Maximum volume [mL] . . .
Termination after n EQPs
.
.
.
.
.
.
.
.
15.0
Yes
• The shape of the titration curve is somewhat af-
n = . . . . . . . . .
Evaluation procedure . .
.
.
.
.
.
.
.
.
1
Standard
fected by the concentration of the indicator. The
Calculation results, however, do not differ significantly.
Result name . . . . . . . . . . . . NiSO4.6H2O
Formula . . . . . . . . . . . . . . R=Q*C/U
Constant . . . . . . . . . . . . . . C=M/z Chemicals
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Rinse
• Buffer solution pH 10: 570 mL 25% NH3 and 70 g
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
. . . . H2O
. . . . 10.0
NH4Cl diluted with deionized water in a 1 L flask.
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
. . . . R1
. . . . Yes
Table of mesured values and E-V curve
Rel. standard deviation srel . . . . Yes
Record
Short-form method . . . . . . . . . Yes
All results . . . . . . . . . . . . Yes
Table of measured values . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Literature
1. METTLER TOLEDO DL70 Applications Bro-
chure No. 1
2. METTLER TOLEDO DL40 Application No. 403
3. METTLER TOLEDO Application No. M066,
M528.
Disposal
Nickel solutions: special waste
Other titrators
DL50 Graphix, DL53/55 (use standard methods)
DL58, DL77. Author: J. v.d. Ouweland, MT-NL
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 81/100
METTLER TOLEDO
Results:
RESULTS
STATISTICS
Number results R1 n = 5
Mean value x = 94.9922 % Silver
Standard deviation s = 0.01715 % Silver
Rel. standard deviation srel = 0.018 %
Outlier test: no outliers!
Page 82/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method AgO2 Purity of AgNO3 Sample Preparation
Version 23-04-1990 10:51
– Clean the sample with acetone and let it dry – use
Title
Method ID . . . . . . . . . . . . . AgO2 tweezers.
Title . . . . . . . . . . .
Date/time . . . . . . . . .
. . . . Purity of AgNO3
. . . . 23-04-1990 10:51
– Weigh in a sample corresponding to approx. 40 mg
Sample Ag and read to ±0.01 mg; then put it in the beaker.
– Add 3 mL of 33% HNO3 and warm up to 60 °C in a
Number samples . . . . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Weight m
Lower limit [g] . . . . . . . . . 0.03
wa-ter bath until the sample is completely dissolved.
Upper limit [g] . . . . . . . . . 0.07 – Let the sample cool down to room temperature and
ID1 . . . . . . . . . . . . . . . . Ag Alloy
Molar mass M . . . . . . . . . . . . 107.868 add 50 mL deion. H2O.
Equivalent number z . . . . . . . . 1
Stir This procedure is prerequisite to achieve high precision.
Speed [%] . . . . . . . . . . . . . 60
Time [s] . . . . . . . . . . . . . . 5
Titration
Titrant . . . . . . . . . . . . . . NaCl
High Precision
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DM-141-SC
Method and preparation are designed for highest preci-
Unit of meas. . . . . . . . . . . . mV sion, i.e. RSD better than 0.050%. Our example shows
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . % nominal content a reproducibility of 0.018% RSD. This high precision is
Metered amount [%] . . . . . . 95.0
Nominal content [%] . . . . . 95.0 required, for example, by mint companies or electronic
Conversion const. . .
Titrant addition . . . .
.
.
.
.
.
.
.
.
M/(10*z)
INC
circuitry manufacturers.
∆V [mL] . . . . . . . . . . . 0.05
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 High Speed
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 The method was also streamlined to fast titrations. The
t(max) [s] . . . . . . . . . . 15.0
Threshold . . . . . . . . . . . . 500.0 titration for one sample takes only approx. 70 seconds.
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard
Calculation Table of measured values
Result name . . . . . . . . . . . . Silver
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) Volume Increment Signal Change 1st deriv. Time
Result unit . . . . . . . . . . . . % mL mL mV mV mV/mL min:s
Decimal places . . . . . . . . . . . 4
Record E1 0.000 215.9 0:03
2.223 2.223 197.4 -18.5 -8.3 0:13
Raw results . . . . . . . . . . . . Yes
3.335 1.112 175.0 -22.4 -20.2 0:21
Table of measured values . . . . . . Yes
E2 3.891 0.556 140.5 -34.5 -62.0 0:29
E - V curve . . . . . . . . . . . . Yes 3.941 0.050 134.7 -5.8 -115.6 0:34
Statistics 3.991 0.050 126.5 -8.2 -163.5 0:40
Ri (i 0 index) . . . . . . . . . . . R1 4.041 0.050 111.0 -15.5 -309.7 0:46
Standard deviation s . . . . . . . . Yes 4.091 0.050 75.6 -35.5 -709.2 0:53
Rel. standard deviation srel . . . . Yes EQP1 4.141 0.050 31.0 -44.6 -891.8 0:59
Outlier test . . . . . . . . . . . . Yes 4.191 0.050 15.0 -16.0 -319.5 1:04
Record 4.241 0.050 5.4 -9.6 -192.1 1:10
All results . . . . . . . . . . . . Yes
E-V curve
Literature
Disposal
Silver precipitate can be separated. The filtrated solu-
tion is neutralized with NaOH.
Other titrators
DL50 Graphix, DL53/55 (use standard methods)
DL58, DL77. Author: Ruth von Rotz, Application laboratory MT Analytical
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 83/100
METTLER TOLEDO
Results:
RESULTS
STATISTICS
Number results R1 n = 3
Mean value x = 112.02 g/L KCN
Page 84/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method BL20 KCN im cy.Ag.Bad
Version 17-02-1994 10:46 Sample preparation
Title
Method ID . . . . . . . . . . . . . BL20
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . KCN im cy.Ag.Bad
. . . . 17-02-1994 10:46
1) 1 mL silver bath is diluted with 50 mL deion-
Sample ized water
Sample no. . . . . . . . . . . . . . 20
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
.
.
.
.
.
.
.
.
1.0 Reaction
Molar mass M . . . . . . . . . . . . 65.12
Equivalent number z . . . . . . . . 2
Temperature sensor . . . . .
Stir
. . . . Manual
• A soluble complex Ag(CN)2 - is first formed by
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
the reaction between silver and cyanide ion:
EQP titration
Titrant . . . . . . . . . . . . . . AgNO3
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DM141-SC
Ag+ + 2 CN- = Ag(CN)2 -
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . to volume As long as free cyanide is still present, the solu-
Volume [mL] . . . . . . . . . 1
Titrant addition . . . . . . . . DYN tion remains clear, but the first excess of silver
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Absolute causes formation of a white solid that mark the
∆V(min) [mL] . . . . . . . 0.05
∆V(max) [mL] . . . . . . . 0.5 endpoint:
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0 Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 50.0
Maximum volume [mL] . . . . . . . 30.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . KCN E-V curve
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Verbrauch
Statistics . . . . . . . . . . . . . Yes
Statistik
Ri (i=Index) . . . . . . . . . . . . R1
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Literature
• Application note, DL25 Application Brochure
"Petroleum and electroplating", ME-51724627.
• Vogel's textbook of quantitative inorganic analy-
sis, 4th edition, Longman Group Limited , 1978.
• D.A. Skoog, D.M. West, "Fundamentals of Ana-
lytical Chemistry", Holt, Rinehart, and Winston,
Disposal 1969.
Cyanide waste • Application no. M525 in Application bro-
chure18, "Standardization of Titrants", 2000.
Other titrators
DL50 Graphix, DL53/DL55/DL58, DL70ES, DL77. Author: Application laboratory, MT Germany
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 85/100
METTLER TOLEDO
Results:
RESULTS
STATISTICS
Number results R1 n = 3
Mean value x = 18.91 g/L
Page 86/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method BL70 Sn-(II) im sauren Sn-Bad
Version 21-02-1994 16:09 Sample preparation
Title
Method ID . . . . . . . . . . . . . BL70
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . KCN im cy.Ag.Bad
. . . . 21-02-1994 16:09
1) 2 mL acidic silver bath is diluted with 50 mL
Sample
Sample no. . . . . . . . . . . . . . 20
deionized water.
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
.
.
.
.
.
.
.
.
2.0
Reaction
Molar mass M . . . . . . . . . . . . 118.71
Equivalent number z . . . . . . . . 2
Temperature sensor . . . . .
Stir
. . . . Manual
• Stannous tin Sn(II) is converted quantitatively
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
into stannic tin Sn(IV) by titration with iodine
EQP titration
Titrant . . . . . . . . . . . . . . 1/2 I2
in the presence of hydrochloric acid:
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DM140-SC
Unit of meas. . . . . . . .
Titration mode . . . . . . .
.
.
.
.
.
.
.
.
mV
EQP
SnCl2 + 2HCl + I2 = SnCl4 + 2 HI
Predispensing 1 . . . . . . . . . to volume
Volume [mL] . . . . . . . . . 0
Titrant addition . . . . . . . . DYN where
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Relative
∆V(min) [%dosVol] . . . . . 0.5
∆V(max) [%buVol] . . . . . 5.0 Sn2+ = Sn4+ + 2 e-
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 I2 + 2 e- = 2 I-
∆t [s] . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 2.0
t(max) [s] . . . . . .
Threshold . . . . . . . .
.
.
.
.
.
.
.
.
20.0
100.0
• Sn(II) is oxidized to Sn(IV) by iodine, and iodine
Maximum volume [mL] . . .
Termination after n EQPs
.
.
.
.
.
.
.
.
50.0
Yes
is reduced to iodide.
n = . . . . . . . . .
Evaluation procedure . .
.
.
.
.
.
.
.
.
1
Standard
• Hydrochloric acid must be present in order to sup-
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
ply chloride ions for the oxidation, otherwise the
Constant . . . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
C=M/z
2
readily hydrolysed Sn(SO4)2 is produced. If nec-
Result unit . . . . . . . . . . . . g/L essary, add 5 mL concentrated HCl.
Result name . . . . . . . . . . . . Sn2+
Statistics . . . . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Statistik
Ri (i=Index) . . . . . . . . . . . . R1
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Application note
Method: 40008
Preparation: 10 mL deionized water
50 mL buffer pH 4.5 Accessories: Titration beakers ME-101974
30 mg Xylenol orange
Indication: DP550 Phototrode with
Titrant: EDTA, DIN-Lemo adapter ME-89600
c(EDTA) = 0.1 mol/L 30 mg Xylenol orange.
Results:
Results n Comments
SO42- :
4.7875 g/L
Page 88/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40008 ZnSO4 in spin-bath
Version 24-01-2001 11:15
• The method was developed on the DL40 titrator
Title
Method ID . . . . . . . . . . . . . 40008
and has been adapted for the DL5x- and DL7x-ti-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . ZnSO4 in spin-bath
. . . 24-01-2001 11:15
trators.
Sample
Sample ID . . . . . . . . . . . . . Spin bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
5.0
• Adjust the DP 550 at 1000 mV in deionised water
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
161.4
1
before starting titration (100% transmission).
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50
Sample preparation
Time [s] . . . . . . . . . . . . . . 15
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . EDTA
1) 5 mL spin bath are diluted in a titration beaker
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DP550
by adding 10 mL deionized water.
Unit of meas. . . . . . . . . . . mV 2) 50 mL buffer solution pH 4.5 are added
Predispensing . . . . . . . . . . . No
Titrant addition . . . . . . . . . . Incremental 3) 30 mg Xylenol orange are added to the sample
∆V [mL] . . . . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . . . Equilibrium controlled solution.
∆E [mV] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0 Reaction
Threshold . . . . . . . . . . . . 200
Steepest jump only . . . . . . . No
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Positive
• Zinc ions form a red complex with xylenol orange
Termination
at maximum volume [mL] . . . . . 20.0
in acidic solution:
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No Zn2+ + Xylenol 2- → Zn-Xylenol
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No By adding EDTA during titration, Zn forms a more
Evaluation
Procedure . . . . . . . . . . . . Standard stable complex with EDTA:
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . .
Stop for reevaluation . . .
.
.
.
.
.
.
No
Yes
Zn-Xylenol + EDTA 4- → Zn-EDTA + Xylenol 2-
Condition . . . . . . . . . . neq=0
Calculation At the equivalence point, all Zn ions have been
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z complexed by EDTA and xylenol orange is free in
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . g/L the acidic solution. There is a colour change from
Result name . . . . . . . . . . . . ZnSO4 Bath cont.
Statistics . . . . . . . . . . . . . Yes red to yellow.
Calculation
Formula . . . . . . . . . . . . . . R2=Q*C2/m
Constant . . . . . . . . . . . . . . C2=96.01/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . g/L Chemicals
Result name . . . . . . . . . . . . SO42- in sample
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ • Buffer solution pH 4.5:
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 4 60 mL glacial acetic acid and 50 g sodium
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption acetateare dissolved in a 1 L volumetric flask.
Statistics . . . . . . . . . . . . . No
Report Dilute to the mark with deionized water.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No Literature
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes • DL40 application note no. 84-22
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No • Applications no. M528 in Application bro-
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No chure18, "Standardization of Titrants", 2000.
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Zinc is precipitated as zinc hydroxide with NaOH or
Ca(OH)2 and then filtrated (precipitate: special waste).
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratoy MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 89/100
METTLER TOLEDO
Results:
Results n Comments
Page 90/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
2-
Method 40009 SO4 in spin-bath
Version 24-01-2001 16:30 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . . . . . 40009
Title . . . . . . . . . . . . . SO42- in spin-bath
trators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Spin bath
Fixed volume
• Adjust the DP 550 at 1000 mV in deionised water
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
.
.
.
.
.
.
1.0
96.01
before starting titration (100% transmission).
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . .
Stir
. . . Manual
Sample preparation
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 30
EQP titration
Titrant/Sensor
1) 1 mL spin bath are diluted in a 100 mL volumetric
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
Ba(ClO4)2
0.005
flask by adding deionized water.
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
DP550
mV
2) 1 mL aliquot is taken and added to the titration bea-
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Yes
3.0
ker.
Wait [s] . . . . . . . . . . . . 20 3) 20 mL deionized water are added.
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.1 4) Add 30 mL acetone.
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 2.0 Steps 3+4: The aqueous mixture is prepared in ad-
∆t [s] . . . . . . . . . . . . . 10.0
t(min) [s] . . . . . . . . . . . 10.0 vance and degassed in an ultrasonic bath before
t(max) [s] . . . . . . . . . . . 45.0
Recognition use. 50 mL are then added to the sample.
Threshold . . . . . . . . . . . . 100
Steepest jump only . . . . . . . No 5) If necessary, acidify the sample to pH 3-6 with
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Negative aqueous perchloric acid 0.05 mol/L.
Termination
at maximum volume [mL] . . . . . 20.0
6) 1 mL mixed indicator is added to the sample prior
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No titration.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation Reaction
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes • Sulphate SO42- is determined by precipitation titra-
Condition . . . . . . . . . . neq=0
Calculation tion with barium perchlorate:
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
2
SO42- + Ba2+ → BaSO4
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
SO42- sample
Yes
• For a better recognition of the endpoint an indica-
Calculation tor is added to the sample solution.
Formula . . . . . . . . . . . . . . R2=Q*100
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . SO42- bath Chemicals
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ
Constant . . . . . . . . . . . . . . • Mixed indicator:
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mL In a 50 mL volumetric flask 0.12 mL 1.6% meth-
Result name . . . . . . . . . . . . Consumption
Statistics . . . . . . . . . . . . . No ylene blue solution and 50 mg Thorin are dis-
Report
Output . . . . . . . . . . . . . . . Printer solved in 5 mL 0.1 mol/L hydrochloric acid. Fill
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes up to the mark with deionized water.
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
.
.
.
.
.
.
Yes
Yes
Literature
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No • DL40 application note no. 84-22
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No • DL40 application no. 106
∆V/∆t - t curve . . . . . . . . . . No
• Applications no. M528 in Application bro-
chure18, "Standardization of Titrants", 2000.
Disposal
Special waste).
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratoy MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 91/100
METTLER TOLEDO
Results:
Results n Comments
Page 92/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
-
Method 40010 F soldering salts
Version 24-01-2001 16:30 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . . . . . 40010
Title . . . . . . . . . . . . . F- soldering salts trators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Soldering salts
Weight Sample preparation
Lower limit [g] . . . . . . . . . 0.8
Upper limit [g] . . . . . . . . . 1.2
Molar mass M . . . . . . . . . . . . 18.998
Equivalent number z . . . . . . . . 3 1) Approx. 1 g soldering salts are dissolved in 150 mL
Titration stand . . . . . . .
Temperature sensor . . . . . .
.
.
.
.
.
.
Stand 1
Manual
deionized water .
Stir
Speed [%] . . . . . . . . . . . . . 50
2) The sample solution is heated at 50°C under stir-
Time [s] . . . . . . . . . . .
EQP titration
. . . 30 ring during 10 minutes.
Titrant/Sensor
Titrant . . . . . . . . . . . . . La(NO3)3
3) After cooling to room temperature, 10 mL buffer
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DX219
pH 6 are added before titration.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
.
.
.
.
.
.
Incremental
0.2
Reaction
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . . 5.0 • Fluoride is precipitated by lanthanum in a slightly
t(max) [s] . . . . . . . .
Recognition
. . . 45.0
acid solution:
Threshold . . . . . . . . . . . . 200
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
3 F- + La3+ = LaF3
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . . . . . 20.0
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No Chemicals
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation • Buffer pH 6 solution:
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No Dissolve approx. 85 g sodium acetate in 1 L deion-
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes ized water. While monitoring the pH value, slowly
Condition . . . . . . . . . . neq=0
Calculation add glacial acetic acid to achieve pH 6.
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) • Titrant solution :
Decimal places . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
.
.
2
%
Dissolve 14.44 g La(NO3)3 • 6H2O in a 1 L volu-
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
% F-
Yes
metric flask and fill up to the mark to obtain the
Calculation
Formula . . . . . . . . . . . . . . R2=Q*C2
concentration c( 1/3 La(NO3)3 ) = 0.1 mol/L.
Constant . . . . . . . . . . . . . . C2=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg
Result name . . . . . . . . . . . . F- sample Literature
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ • DL40 application note no. 8317
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 4 • DL40 application no. 102.
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption
• Jander, Jahr, "Massanalyse", elaborated by
Statistics . . . . . . . . . .
Report
. . . No
Gerhard Schulze and Jürgen Simon, 14th edition,
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No
Walter de Gruyter, Berlin New York, 1986.
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratory MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 93/100
METTLER TOLEDO
Sample: NaF 0.1 mol/L standard solution, Instruments: METTLER TOLEDO DL53
2.5 mL Matrix printer Epson LX800
with serial inteface 8148
Substance: F - , M = 18.998, z = 2 AT261
Results:
Results n Comments
Page 94/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40011
Version
Titer Pb(NO3)2
26-01-2001 10:12
• The method was developed on the DL40 titrator
Title
and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . 40011
. . . Titer Pb(NO3)2
trators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
NaF 0.1 M
Fixed volume
Sample preparation
Volume [mL] . . . . . . . . . . . 2.5
Molar mass M . . . . . . . . . . . . 18.998
Equivalent number z . . . . . . . . 2 1) The standard solution is prepared by dissolving
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual 4.200 g NaF in a 1 L volumetric flask and filling up
Stir
Speed [%] . . . . . . . . . . . . . 50 to 1 L with deionized water.
Time [s] . . . . . . . . . . . . . . 30
EQP titration The fluoride solution is kept in polyethylene
Titrant/Sensor
Titrant . . . . . . . . . . . . . 1/2Pb(NO3)2 bottles.
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DX219 2) 5 mL of the standard solution are diluted with 20
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . Yes mL deionized water, 20 mL isopropanol and 5 mL
Volume [mL] . . . . . . . . . . . 4.5
Wait [s] . . . . . . . . . . . . 30 0.5 mol/L NaCl.
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.5 Reaction
∆t [s] . . . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . . . . . 45.0
Recognition • Fluoride is precipitated by lead according to:
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No 2 F- + Pb2+ = PbF2
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . . . . . 20.0
• This method can be used for the titration of sul-
at potential . . . . . . .
at slope . . . . . . . . .
.
.
.
.
.
.
No
No
phate ions.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
.
.
.
.
.
.
Standard
No
Chemicals
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 • Titrant solution :
Calculation
Formula . . . . . . . . . . . . . . R=m/(VEQ*c*C) Dissolve 16.56 g Pb(NO3)2 in a 1 L volumetric
Constant . . . . . . . . . . . . . . C=1/(0.1*z)
Decimal places . . . . . . . . . . . 5 flask and fill up to the mark to obtain the concentra-
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Titer tion c( 1/2 Pb(NO3)2 ) = 0.1 mol/L
Statistics . . . . . . . . . . . . . Yes
Titer
Titrant . . . . . . . . . . . . . . 1/2Pb(NO3)2
Concentration . . . . . . . . . . . 0.1 Literature
Formula t . . . . . . . . . . . . x
Report
Output . . . . . . . . . . . . . . . Printer • DL40 application no. 102.
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes • C.E. Efstathion, T.P. Hadjhoannon,
Raw results . . . . . . . . .
Table of measured values . . .
.
.
.
.
.
.
No
Yes
Anal. Chim. Acta 109 (1979), p. 319.
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratory MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 95/100
Literature
3) Peter Wolfram Wild, "Modern Analysis for Electroplating", Hampton Hill Finishing Publica-
tions, 1974.
Peter Wolfram Wild, "Moderne Analyse für die Galvanotechnik", Eugen G. Leuze Verlag,
Saulgau (Württemberg), Germany , 1972. (Geman)
6) "Galvanik von A bis Z", Application brochure from Mettler-Toledo Germany (German), 1995,
ME-99 407 55.
Internet:
Titration homepage of METTLER TOLEDO:
http://www.titration.net
Check also the application database at this Internet address.
Page 96/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Notes
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 97/100
This applications brochure represents selected, possible application examples. These have been tested with all possible
care in our lab with the analytical instruments mentioned in the bulletin. The experiments were conducted and the
resulting data evaluated based on our current state of knowledge.
However, the applications brochure does not absolve you from personally testing its suitability for your intended meth-
ods, instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot
accept any responsibility for the use or consequences of the applications contained in this brochure.
When chemicals and solvents are used, the general safety rules and the directions of the producer must be
observed.
Page 98/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Mettler-Toledo GmbH
Analytical
CH-8603 Schwerzenbach, Schweiz
Telefon (01) 806 77 11, Fax (01) 806 73 50
Internet: http://www.mt.com