METTLER TOLEDO Titrators
Electronics and
electroplating applications
Application brochure 28
Dear Reader
Information technology and electronics have become increasingly relevant in our society
deeply influencing every aspect of our life. In particular, the world of communication has
experienced the largest transformation: thanks to powerful computers, Internet and mobile
phones the way of communicating has become faster, and an exponentially increasing
amount of information has become available.
If software is the soul of electronics devices, hardware represents their body. They can
smoothly function if their components such as printed circuits meet the required quality
standards. The production quality can be monitored by a variety of analytical techniques.
Titration is one analytical method used in electroplating and electronics industry to mainly
control the metal ion content and the degree of acidity of electroplating baths.
42 different methods covering various determinations in the electroplating analysis
are presented in this brochure, a representative collection of widely used titrations in the
electroplating and electronics industry.
These applications are the result of the efforts of many people. First we would like to mention
our former Applications Chemist Kees Mooibroek. His work from the previous application
brochure 4 “electroplating” was included in the present brochure, and completed with the
applications on titration of gold and silver. From collaboration with customers and our selling
organizations we were able to get additional methods, and Applications chemists extensively
tested the applications in the Market Support Laboratory.
We are proud to present to you our brochure on applications in the electroplating and
th
electronics industry containing valuable information and practical hints. This is the 28
brochure of a long series of comprehensive applications, which continues the tradition started
since the early 1970’s to focus on analytical competence in Market Support Group.
We wish you a lot of success
Craig Gordon
Manager Market Supporrt AnaChem
Cosimo A. De Caro
Applications Chemist
Contents
M062
Electroless copper bath: Determination of copper ....................................................... 4
M063
Electroless copper bath: Determination of free complexing agents ............................. 6
M064
Electroless copper bath: Sodium hydroxide and formaldehyde ................................... 8
M065
Electroless nickel bath: Determination of sodium hypophosphite ............................. 12
M066
Electroless nickel bath: Determination of nickel ....................................................... 16
M067
Electroless nickel bath: Determination of sodium orthophosphite ............................ 18
M151
Determination of acetic, phosphoric and nitric acid in a mixture .............................. 20
M152
Nitric, acetic and phosphoric acid mixture: large excess of phosphoric acid ............ 22
M153
Nitric, acetic and phosphoric acid mixture: concentrations below 0.3% ................... 24
M154
Simultaneous titration of HCl, CH3COOH, and NH4Cl ............................................. 26
M155
Polishing bath: determination of sulfuric and phosphoric acid .................................. 28
M156
Determination of boric acid in acidic mixtures of HCl and HF ................................. 30
M157
Determination of hydrochloric and nitric acid ........................................................... 34
M158
Determination of ammonia and hydrogen peroxide ................................................... 36
M159
Determination of hydrochloric acid and hydrogen peroxide ..................................... 38
M181
Back-titration of aluminum in acidic bath.................................................................. 40
M182
Titration of sulphuric and aluminum in an electroplating bath .................................. 42
M183
Determination of nickel and cadmium by complexometry ........................................ 44
M184
Determination of cadmium in alkaline bath ............................................................... 46
M185
Iodometric titration of Cr(VI) in an electroplating bath ............................................. 48
M186
Determination of Cr(III) by back-titration in an electroplating bath ........................ 50
M187
Chromium and vanadium in a K2Cr2O7 / V2O5 mixture ............................................. 52
M188
Determination of Cr(VI) in an electroplating bath by Fe(II) titration ........................ 54
M189
Determination of free cyanide in a copper bath ......................................................... 56
Page 2/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
M190
Determination of free cyanide in a cyanidic zinc bath ............................................... 58
M191
Back-titration of zinc in a cyanidic zinc bath ............................................................. 60
M175
Titration of gold -Au(III)- in a standard solution ....................................................... 62
M208
Determination of gold by precipitation reaction with hydroquinone ......................... 64
M209
Titer determination of cerium sulfate vs. hydroquinone ........................................... 66
M210
Standardization of hydroquinone with pure gold ....................................................... 68
M179
Determination of the gold content in alloy................................................................. 72
M180
Determination of the approximate gold content content in alloys ............................. 75
M192
Determination of lead(IV) in batteries ...................................................................... 76
M193
Complexometric titration of lead in alloy .................................................................. 78
M194
Determination of nickel in an electroplating bath ...................................................... 80
M195
Determination of silver in silver alloy........................................................................ 82
M196
Determination of free potassium cyanide in a silver bath .......................................... 84
M197
Titration of Tin(II) in acidic tin bath .......................................................................... 86
M198
Photometric titration of zinc in a spin bath ................................................................ 88
M199
Determination of sulphate in a spin bath by precipitation titration ............................ 90
M200
Titration of fluoride in soldering salts ........................................................................ 92
M201
Standardization of 1/2 Pb(NO3)2 ............................................................................... 94
Literature
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 3/100
METTLER TOLEDO
M062
Electroless copper bath: Determination of copper
Sample:
Electroless copper bath
10 mL
Substance:
Copper (II),
M = 63.546, z = 1
Instruments: METTLER TOLEDO DL70
Matrix Printer Epson LX800
with serial interface 8148
Method:
Preparation: 40 mL sulphuric acid 25%
5 mL Potassium iodide 10 %
5 mL Potassium thiocyanate 10%
Titrant:
Sodium thiosulphate, Na2 S2O3
c(Na2 S2O3) = 0.1 mol/L
Standard:
Potassium iodate, KIO3
(see application M009)
Results:
METTLER DL70
062
Accessories: Titration beakers ME-101974
Indication:
Titrator
DM140-SC at Sensor 2
* METTLER - TOLEDO *
Application Laboratory
062
Chem. Copper Electrolyte
20-Jun-1991 11:28
SW Version 2.0
measured
Titrator
User
20-Jun-1991 13:20
Electroplating
**** KM ****
RESULTS
No
Identification
Volume
Results
1/1
CHEM Cu
MD &/2
10.0 mL
1/2
CHEM Cu
MD &/2
10.0 mL
1/3
CHEM Cu
MD &/2
10.0 mL
1/4
CHEM Cu
MD &/2
10.0 mL
1/5
CHEM Cu
MD &/2
10.0 mL
1.390
3.490
5.460
1.407
3.534
5.529
1.398
3.512
5.494
1.395
3.504
5.482
1.373
3.449
5.396
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers
Page 4/100 METTLER TOLEDO DL5x and DL7x Titrators
n
x
s
srel
=
=
=
=
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
5
1.393 g/L
0.0126
0.902 %
Copper (Cu)
CuSO4
CuSO4.5H2O
Copper (Cu)
CuSO4
CuSO4.5H2O
Copper (Cu)
CuSO4
CuSO4.5H2O
Copper (Cu)
CuSO4
CuSO4.5H2O
Copper (Cu)
CuSO4
CuSO4.5H2O
Copper (Cu)
g/L
Copper (Cu)
Electronics and electroplating applications
Method
Method
062
Version
Chem. Copper Electrolyte
20-Jun-1991 11:28
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆V [mL] . . . . . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
EQP range
. . . . . . .
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
Result last sample . . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . 062
. . . . Chem. Copper Electrolyte
. . . . 20-Jun-1991 11:28
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5
Stand 1
Fixed volume U
10.0
********
0.0
1
. . . . 40
. . . . 10
Remarks
Bath composition
This bath is used for chemical copper deposition on
printed circuit boards. It consists of sodium hydroxide, formaldehyde, weakly complexed copper, free
complexing agent(s), and additives.
Sample preparation
Be careful! If cyanide is present in the sample, the
addition of a sulphuric acid solution must be performed
in a ventilated fume hood (formation of HCN!).
1) A weak copper complex is decomposed at room
temperature by the acid medium. A stronger complex is decomposed in the same way at elevated
temperature.
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Na2S2O3
0.1
DM140-SC
mV
EQP
mL
1.0
INC
0.1
EQU
0.5
2.0
3.0
30.0
100.0
Yes
800.0
0.0
20.0
Yes
1
Standard
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Copper (Cu)
R1=Q*C1/U
C1=63.546/z
g/L
3
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CuSO4
R2=Q*C2/U
C2=159.60/z
g/L
3
The amount of iodine formed is proportional to the
Cu(II) content. Cover the beakers to avoid loss of
iodine
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CuSO4.5H2O
R2=Q*C2/U
C2=249.68/z
3
5) The complete reduction of Cu(II) requires 5 min.
. . . . Printer
. . . . Yes
. . . . Yes
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R1
Yes
Yes
Yes
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Literature
2) After decomposition the sample is cooled at room
temperature.
3) Then potassium iodide (KI) and potassium thiocyanate (KSCN) are added.
4) Cu(II) is reduced with excess iodide (I-) and subsequently precipitated as CuI in the presence of
thiocyanate (SCN-). KSCN is added to avoid adsorption of I2 on the surface of CuI :
2 Cu2+ + 4 I - → 2 CuI + I2
Titration of iodine
I2 is titrated at room temperature with Na2S2O3:
2 S2O32- + I2 → S4O62- + 2 I• Stir moderately. Vigorous stirring causes loss of
I2
• Alternative: Photometric indication with DP550
Phototrode; indicator: starch
• Titration time: approx. 4 minutes
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.
Electronics and electroplating applications
Author:
Kees Mooibroek
METTLER TOLEDO DL5x and DL7x Titrators Page 5/100
METTLER TOLEDO
M063
Electroless copper bath: Determination of free complexing agents
Sample:
Electroless copper bath
5 mL
Substance:
Complexing agents
Instruments: METTLER TOLEDO DL70
Matrix Printer Epson LX800
with serial interface 8148
Preparation: 60 mL deionised water
Titrant:
Copper sulphate, CuSO4
c(CuSO4) = 0.01 mol/L
Standard:
EDTA
(see application M007)
Results:
METTLER DL70
063
Method:
Accessories: Titration beakers ME-101974
DP550 Phototrode at sensor 2
DIN-Lemo Adapter ME-89600
Indicator:
0.25 g Murexide, 1:500 trituration with NaCl
Indication:
Mettler-Toledo AG
Application Laboratory
Titrator
063
Free Complexing Agents
23-Jul-1991 15:25
SW Version 2.0
measured
Titrator
User
23-Jul-1991
P5
KM
16:24
RESULTS
No
Identification
Volume
Results
1/1
1/2
1/3
1/4
1/5
Chem.Cu
Chem.Cu
Chem.Cu
Chem.Cu
Chem.Cu
5.0
5.0
5.0
5.0
5.0
20.408
20.412
20.391
20.414
20.408
MD
MD
MD
MD
MD
6/8
6/8
6/8
6/8
6/8
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test : sample No.
Statistics without sample No.
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Page 6/100 METTLER TOLEDO DL5x and DL7x Titrators
mL
mL
mL
mL
mL
n
x
s
srel
mmol/L
mmol/L
mmol/L
mmol/L
mmol/L
= 5
= 20.407 mmol/L
= 0.0089 mmol/L
= 0.044 %
1/3
1/3
n = 4
x = 20.411 mmol/L
s = 0.0029 mmol/L
srel = 0.014 %
Free
Free
Free
Free
Free
Compl.
Compl.
Compl.
Compl.
Compl.
Free Compl.
Free Compl.
Free Compl.
Free Compl.
Electronics and electroplating applications
Method
Method
063
Version
Remarks
Free Complexing Agents
23-Jul-1991 15:25
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆V [mL] . . . . . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
EQP range
. . . . . . .
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
Result last sample . . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . 063
. . . . Free Complexing Agents
. . . . 23-Jul-1991 15:25
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5
Stand 1
Fixed volume U
10.0
********
0.0
1
. . . . 40
. . . . 10
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CuSO4-(2)
0.01
DP550
mV
EQP
mL
0.0
INC
0.1
EQU
2.0
2.0
3.0
30.0
100.0
Yes
0.0
1000.0
40.0
Yes
1
Standard
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Free compl.
R1=Q*C1/U
C1=1000
mmol/L
3
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R1
Yes
Yes
Yes
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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
Bath composition
• This bath is used for chemical copper deposition
on printed circuit boards. It consists of sodium hydroxide, formaldehyde, weakly complexed copper,
free complexing agent(s), and additives.
• Depending on the use of the bath a single specific
complexing agent or a mixture of various complexing agents is used. Results are given in mmol/L.
• The free complexing agents influence the rate of
copper deposition and the stability of the bath.
Sample preparation
1) The copper bath is diluted and then titrated with
0.01 M Cu(II) titrant. No pH buffer is added, the
sample is alkaline.
2) It is recommended to use a trituration 1:500 murexide: NaCl.
3) Add the indicator before starting analysis. Keep
sample free of air bubbles during titration. Air
bubbles and undissolved impurities affect with the
photometric indication.
Titration
Free complexing agents are titrated with Cu(II)-solution in alkaline solution:
Cu 2+ + Agent → Cu-Agent 2+
At the equivalence point (simplified):
Cu 2+ + Murexide - → Cu-Murexid + (violet-yellow)
• Adjust the DP 550 at 1000 mV in deionised water
before starting titration (100% transmission).
• Due to the steep signal change, an EQP titration
with fixed increments is used. The low threshold
value allows for different amounts of indicator.
• A fixed predispensing shortens the titration time.
• Titration time: approx. 4 minutes.
E-V curve
Copper solutions: special waste
Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators.
Author:
Electronics and electroplating applications
Kees Mooibroek
METTLER TOLEDO DL5x and DL7x Titrators Page 7/100
METTLER TOLEDO
M064
Electroless copper bath: Sodium hydroxide and formaldehyde
Sample:
Electroless copper bath
5 mL
Substance:
Sodium hydroxide, formaldehyde
Instruments: METTLER TOLEDO DL70
Matrix Printer Epson LX800
with serial interface 8148
Preparation: Deionised water, 40 mL
Titrant 1:
Titrant 2:
Standard:
Results:
064
Method:
Accessories: Titration beakers ME-101974
1 additional DV90 burette drive
1 additional DV1010 burette
Hydrochloric acid, HCl,
c(HCl) = 0.1 mol/L
Sodium sulfite, Na2SO3
c(Na2SO3) = 1 mol/L (pH = 10.5)
DG111-SC at sensor 1
Indication:
Tris(hydroxymethyl)aminomethane
064
Hydroxide and Formaldehyde
18-Jun-1991 11:05
SW Version 2.0
measured
Titrator
User
18-Jun-1991
P5
KM
17:18
RESULTS
No
Identification
Volume
1/1
Chem.Cu
MD 4/7
5.0
mL
1/2
Chem.Cu
MD 4/7
5.0
mL
1/3
Chem.Cu
MD 4/7
5.0
mL
1/4
Chem.Cu
MD 4/7
5.0
mL
1/5
Chem.Cu
MD 4/7
5.0
mL
STATISTICS
Number results
Mean value
STATISTICS
Number results
Mean value
Standard deviation
Rel. standard deviation
Outlier test : no outliers!
STATISTICS
Number results
Mean value
Standard deviation
Rel. standard deviation
Outlier test : no outliers!
Page 8/100 METTLER TOLEDO DL5x and DL7x Titrators
R1
Results
12.2
14.59
-0.59
8.69
-0.19
12.3
14.55
-0.62
8.60
-0.10
12.2
14.62
-0.62
8.60
-0.10
12.2
14.51
-0.51
8.54
-0.04
12.2
14.52
-0.52
8.41
0.09
pH
g/L
g/L
g/L
g/L
pH
g/L
g/L
g/L
g/L
pH
g/L
g/L
g/L
g/L
pH
g/L
g/L
g/L
g/L
pH
g/L
g/L
g/L
g/L
n = 5
x = 12.2
pH
Dil. sample
NaOH
Correction
Formaldehyde
Correction
Dil. sample
NaOH
Correction
Formaldehyde
Correction
Dil. sample
NaOH
Correction
Formaldehyde
Correction
Dil. sample
NaOH
Correction
Formaldehyde
Correction
Dil. sample
NaOH
Correction
Formaldehyde
Correction
Dil. sample
R2
n = 5
x = 14.56
s = 0.047
srel = 0.319
g/L
mmol/L
%
NaOH
R4
n = 5
x = 8.58
s = 0.109
srel = 1.273
g/L
g/L
%
Formaldehyde
Formaldehyde
Electronics and electroplating applications
Method
Method
1
2
3
4
5
6
064
Version
Hydroxide and Formaldehyde
18-Jun-1991 11:05
Title
Method ID . . . . . . . . . . . . . 064
Title . . . . . . . . . . . . . . . Hydroxide and
Formaldehyde
Date/time . . . . . . . . . . . . . 18-Jun-1991 11:05
Instruction
Instruction . . . . . . . . . . . . Analysis to be done
> . . . . . . . . . . . . . . . . . after correction of
> . . . . . . . . . . . . . . . . . the copper content.
Sample
Number samples
. . . . . . . . . . 5
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 5.0
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z . . . . . . . . 1
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
Measure
Sensor
. . . . . . . . . . . . . . DG111-SC-(2)
Unit of meas . . . . . . . . . . . . As installed
∆E [mV] . . . . . . . . . . . . . . 0.5
∆t [s]
. . . . . . . . . . . . . . 3.0
t(min) mode . . . . . . . . . . . . Fix
t(min) [s] . . . . . . . . . . . 30.0
t(max) [s]
. . . . . . . . . . . . 300.0
Calculation
Result name . . . . . . . . . . . . Dil. sample
Formula . . . . . . . . . . . . . . R1=E
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . pH
Decimal places . . . . . . . . . . . 1
Titration
Titrant . . . . . . . . . . . . . . HCl
Concentration [mol/L] . . . . . . . 0.1
Sensor
. . . . . . . . . . . . . . DG111-SC-(2)
Unit of meas . . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EP
Predispensing . . . . . . . . . . mL
Volume [mL] . . . . . . . . . 1.0
Titrant addition . . . . . . . . Continuous
Control band [mV, pH,...]. . . 0.3
Delay [s] . . . . . . . . . . 10
End point mode . . . . . . . . . EPA
Potential [mV, pH,...] . . . . 10.5
Tendency . . . . . . . . . . . . Negative
Maximum volume [mL] . . . . . . . 30.0
Calculation
Result name . . . . . . . . . . . . NaOH
Formula . . . . . . . . . . . . . . R2=Q1*C2/U
Constant . . . . . . . . . . . . . . C2=40/1
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Calculation
Result name . . . . . . . . . . . . Correction
Formula . . . . . . . . . . . . . . R3=14-(Q1*C3)/U
Constant . . . . . . . . . . . . . . C3=40/1
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Record
Output unit . . . . . . . . . . . . Printer
Result last sample . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Dispense
Titrant . . . . . . . . . . . . . . Na2SO3 (pH 10.5)
Concentration [mol/L] . . . . . . . 1.0
Volume [mL]. . . . . . . . . . . . . 10.0
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>0
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>0
Titration
Titrant . . . . . . . . . . . . . . HCl
Concentration [mol/L] . . . . . . . 0.1
Sensor
. . . . . . . . . . . . . . DG111-SC-(2)
Unit of meas . . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EP
Predispensing . . . . . . . . . . mL
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . Continuous
Control band [mV, pH,...]. . . 0.2
Delay [s] . . . . . . . . . . 10
End point mode . . . . . . . . . EPA
Potential [mV, pH,...] . . . . 10.5
Tendency . . . . . . . . . . . . Negative
Maximum volume [mL] . . . . . . . 30.0
Condition . . . . . . . . . . . . Yes
Electronics and electroplating applications
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Condition . . . . . . . . .
Condition . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Record
Output unit . . . . . . . .
Result last sample . . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
.
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.
.
Formaldehyde
R4=Q[2]*C4/U
C4=30.03/1
g/L
2
Yes
R2>0
7
.
.
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.
.
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.
.
.
.
Correction
R5=8.5-(Q[2]*C5/U)
C5=30.03/1
g/L
2
Yes
R2>0
8
.
.
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.
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.
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.
.
.
Sodium hydroxide
content too high.
***PLEASE CORRECT***
Yes
R2>16
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Sodium hydroxide
content too low.
***PLEASE CORRECT***
Yes
R2<12
.
.
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.
.
.
.
.
.
.
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.
.
.
.
.
.
Formaldehyde content
too high
***PLEASE CORRECT***
Yes
R4>10
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Formaldehyde content
too low
***PLEASE CORRECT***
Yes
R4<7
. . . . Printer
. . . . Yes
. . . . Yes
. . . . R1
.
.
.
.
.
.
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.
.
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.
R2
Yes
Yes
Yes
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R4
Yes
Yes
Yes
. . . . Printer
. . . . Yes
Remarks
• The electrode DG111-SC is calibrated in the
range of pH 9 to 12 (see application M004).
• Hydrochloric acid is standardized with THAM
(see application M003).
• The pH value of the sodium sulphite solution
(Titrant 2) has to be adjusted to the same endpont value as in the titration (see 6). Otherwise
complicated blank evaluations are necessary.
• Total analysis time: approx. 4 minutes.
• The titrator displays warnings if upper or lower
result limits are exceeded.
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 literature of the manufacturer. No overtitration. This titration allows the determination of the NaOHcontent.
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:
HCHO
+
Na2SO3
+
H2O
→
CH2OH•SO3Na
+
NaOH
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 concetration 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.
Author:
Electronics and electroplating applications
Kees Mooibroek
METTLER TOLEDO DL5x and DL7x Titrators Page 11/100
METTLER TOLEDO
M065
Electroless nickel bath: Determination of sodium hypophosphite
Sample:
Electroless nickel bath
3 mL
Substance:
Standard:
For Na2S2O3: Potassium iodate
Instruments: METTLER TOLEDO DL70
Sodium hypophosphite monohydrate,
Matrix Printer Epson LX800
NaH2PO2 • H2O, M = 105.99
with serial interface 8148
Preparation: - H2SO4 (20%), 50 mL
- I2 , c(1/2 I2) = 0.1 mol/L, 20 mL
- Oxidation reaction time: 60 min
(in the dark)
Method:
065a, 065b
Titrant 1:
Iodine, I2 , c(1/2 I2) = 0.1 mol/L,
Accessories: Titration beakers ME-23828
(brown glass beaker)
1 additional DV90 burette drive
1 additional DV1010 burette
Titrant 2:
Na2S2O3 , c(Na2S2O3)= 0.1 mol/L
Indication:
Results:
065a Hypophosphite in Chem.Ni
18-Nov-1991 14:51
SW Version 2.0
measured
Titrator
User
DM140-SC at sensor 2
18-Nov-1991
P 5
KM
15:28
RESULTS
No
Identification
1/1
Chem.Ni
13/40
3.0
mL
1/2
Chem.Ni
13/45
3.0
mL
1/3
Chem.Ni
13.50
3.0
mL
1/4
Chem.Ni
13.55
3.0
mL
1/5
Chem.Ni
13.60
3.0
mL
STATISTICS
Number results
Mean value
Volume
R1
STATISTICS
Number results
R2
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
STATISTICS
Number results
Mean value
R3
Page 12/100 METTLER TOLEDO DL5x and DL7x Titrators
Results
29.06
35.01
-9.01
28.93
34.85
-8.85
29.10
35.06
-9.06
29.26
35.25
-9.25
29.00
34.94
-8.94
n = 5
x = 29.07
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
NaH2PO2
NaH2PO2•H2O
Correction
NaH2PO2
NaH2PO2•H2O
Correction
NaH2PO2
NaH2PO2•H2O
Correction
NaH2PO2
NaH2PO2•H2O
Correction
NaH2PO2
NaH2PO2•H2O
Correction
g/L
NaH2PO2
5
35.02
0.150
0.428
g/L
g/L
%
NaH2PO2•H2O
NaH2PO2•H2O
n = 5
x = -9.02
g/L
Correction
n
x
s
srel
=
=
=
=
Electronics and electroplating applications
Method 065a / Content determination
Method
065a
Version
Hypophosphite in Chem.Ni
18-Nov-1991 14:51
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set)[mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
∆V(max) [%buVol]. .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
EQP range
. . . . . . .
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Record
Output unit . . . . . . . .
Result last sample . . . . .
Table of measured values . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . 065a
. . . . Hypophosphite in Chem.Ni
. . . . 18-Nov-1991 14:51
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5
Stand 1
Fixed volume U
3.0
********
89.978
2
. . . . 40
. . . . 5
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Na2S2O3
0.1
DM140-SC
mV
EQP
mL
0.0
DYN
8.0
Relative
0.5
2.5
EQU
1.0
3.0
3.0
30.0
150.0
Yes
1000.0
-1000.0
30.0
Yes
1
Standard
.
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.
NaH2PO2
R1=(H3-Q1)*C1/U
C1=M/z
g/L
2
.
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.
.
NaH2PO2•H2O
R2=(H3-Q1)*C2/U
C2=105.99/z
g/L
2
.
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.
.
Correction
R3=26-((H3-Q1)*C3/U)
C3=105.99/1
g/L
2
.
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.
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.
.
.
.
.
.
Sodium hypophosphite
monohydrate content
too high.Pls.correct
Yes
R2>29
.
.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Sodium hypophosphite
monohydrate content
too low.Pls.correct
Yes
R2<23
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Printer
Yes
Yes
Yes
. . . . R1
.
.
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.
.
R2
Yes
Yes
Yes
.
.
.
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.
.
.
.
.
.
.
R4
Yes
Yes
Yes
. . . . R3
Remarks
Bath composition
• This bath consists of nickel salts, sodium hypophosphite, buffering compounds, stabilisers,
accelerators, wetting and complexing agents.
Decomposition products are formed during use
of the bath.
Sample preparation (Method 065a)
1) 2 mL sample are diluted with 50 mL sulphuric
acid solution 20%.
2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
dispensed with a burette ("Titrant 1") to the
acidified sample using the auxiliary function
"Dosing" of the titrator. After dispensing cover
the titration beaker by e.g. a watch glass.
3) This oxidation is carried out at room temperature in the dark. Cover the beaker to prevent
loss of iodine:
I2 + H2PO2- + H2O = 2I- + HPO32- +3H+
The reaction requires 60 minutes to complete.
4) Oxidising agents stronger than iodine may
cause side reactions with organic bath components or decomposition products.
5) The amount of substance of the dispensed iodine solution is determined with method 065b
(see next page).
Content determination (Method 065a)
1) The content of sodium hypophosphite is determined by an iodometric backtitration. Excess
iodine is dispensed (sample preparation) in
order to oxidise hypophosphite in the acidic
solution. The remaining excess iodine is titrated with sodium thiosulphate:
I2 + 2 S2O32-
→ 2I- + S4O62-
2) Sodium thiosulphate is standardized with potassium iodate (see application M009).
3) The titrator displays warnings if upper or lower
result limits are exceeded.
. . . . Printer
. . . . Yes
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 13/100
Results and table of measured values
065a Hypophosphite in Chem.Ni
18-Nov-1991 14:51
SW Version 2.0
measured
Titrator
User
18-Nov-1991
P 5
KM
15:19
RESULTS
No
Identification
1/1
Chem.Ni
13.55
Volume
3.0
SAMPLE
No. 1/4
Titration stand
Identification
Chem.Ni
Volume
Correction factor
MEASURED VALUES
Titrant
Drive
Sensor
E1
E2
EQP1
Results
Na2S2O3
Drive 2
DM140-SC
mL
29.26
35.25
-9.25
g/L
g/L
g/L
NaH2PO2
NaH2PO2•H2O
Correction
Stand 1
13.55
U = 3.0 mL
f = 1.0
0.1 mol/L
20 mL
t = 0.99896
Volume
mL
Increment
mL
Signal
mV
Change
mV
1st deriv.
mV/mL
Time
min:s
0.0000
0.0040
0.0080
0.0120
0.0220
0.0480
0.1120
0.1280
0.1420
0.1500
0.1540
0.1580
0.1620
0.1660
0.0040
0.0040
0.0040
0.0100
0.0260
0.0640
0.0160
0.0140
0.0080
0.0040
0.0040
0.0040
0.0040
284.0
283.8
283.4
283.3
283.2
281.8
264.0
264.0
256.0
242.7
221.9
191.0
179.6
178.7
-0.2
-0.4
-0.2
-0.1
-1.4
-17.9
0.0
-8.0
-13.3
-20.8
-30.9
-11.4
-1.0
-52.5
-94.5
-38.5
-5.6
-53.8
-278.9
1.8
-568.0
-1664.2
-5211.4
-7720.9
-2838.4
-241.5
0:03
0:07
0:12
0:15
0:19
0:26
0:36
0:40
0:49
0:56
1:17
1:48
2:08
2:11
Method 065a / Content determination
Page 14/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method 065b / Iodine solution
Method
065b
Version
Aux. value for M065/M067
19-Nov-1991 14:12
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Dispense
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set)[mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
∆V(max) [%buVol]. .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
EQP range
. . . . . . .
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
Results last sample . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Auxiliary value
ID text . . . . . . . . . .
Formula . . . . . . . . . .
Condition . . . . . . . . .
Condition
. . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . 065b
. . . . Aux. value for M065/M067
. . . . 19-Nov-1991 14:12
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3
Stand 1
Fixed volume U
0.0
********
0.0
1
. . . . 40
. . . . 5
. . . . 1/2 I2
. . . . 0.1
. . . . 20.0
. . . . 40
. . . . 20
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Na2S2O3
0.1
DM140-SC
mV
EQP
mL
15.0
DYN
4.0
Relative
0.1
1.5
EQU
1.0
3.0
3.0
30.0
150.0
Yes
1000.0
-1000.0
30.0
Yes
1
Standard
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Consumption
R1=Q1
Remarks
Sample preparation Method 065b
1) 50 mL sulphuric acid solution 20% are given
into a titration beaker.
2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
dispensed automatically by the titrator using
the function "Dispense" in method 065b.
Titration
1) Iodine is titrated with sodium thiosulphate:
I2 + 2 S2O32-
→ 2 I- + S4O62-
2) Sodium thiosulphate is standardized with potassium iodate (see application M009).
3) The mean value of a series of three sample is
automatically stored as auxiliary value H3 and
can therefore by applied by method 065a for
the determination of nickel.
4) The storage of the mean value only occurs if
it is comprised between the limits 1.5 and 2.5
mmol which assure an adequate cocnentration.
5) The shelf life of the iodine solution is limited.
We recommend to perfom method 065b before
mmol
4
. . . . Printer
. . . . Yes
. . . . Yes
. . . . R1
. . . . Yes
. . . . Yes
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Aux.M065/M067
H3=�[1]
Yes
1.5<�<2.5
. . . . Printer
. . . . Yes
Method 065b / Iodine concentration
Disposal
Nickel solutions: special waste
Other titrator
DL77 titrator.
Author:
Electronics and electroplating applications
Kees Mooibroek
METTLER TOLEDO DL5x and DL7x Titrators Page 15/100
METTLER TOLEDO
M066
Electroless nickel bath: Determination of nickel
Sample:
Electroless nickel bath
5 mL
Substance:
Nickel, M = 58.69 g/mol
Instruments: METTLER TOLEDO DL70
Matrix Printer Epson LX800
with serial interface 8148
Method:
Preparation: - Deionised water, 50 mL
- Buffer pH 10, 10 mL
- 0.25 g Murexide trituration
with NaCl (1:500).
Titrant:
EDTA, c(EDTA) = 0.1 mol/L
Standard:
Zinc sulfate, c(ZnSO4) = 0.1 mol/L
(See METTLER method M007)
066
Accessories: Titration beakers ME-101974
Indication:
- DP550 Phototrode at sensor 2
- Indicator: Murexide trituration
Results:
066 Ni in Chem. Ni-Electrolyte
13-Sep-1991 13:39
SW Version 2.0
measured
Titrator
User
13-Sep-1991
P5
KM
14:23
RESULTS
No
Identification
1/1
1/2
1/3
1/4
1/5
1/6
CHEM.Ni
CHEM.Ni
CHEM.Ni
CHEM.Ni
CHEM.Ni
CHEM.Ni
LR-200
LR-200
LR-200
LR-200
LR-200
LR-200
Volume
5.0
5.0
5.0
5.0
5.0
5.0
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
Page 16/100 METTLER TOLEDO DL5x and DL7x Titrators
Results
mL
mL
mL
mL
mL
mL
n
x
s
srel
=
=
=
=
5.75
5.74
5.77
5.75
5.74
5.73
g/L
g/L
g/L
g/L
g/L
g/L
6
5.74
0.012
0.211
g/L
g/L
%
Ni
Ni
Ni
Ni
Ni
Ni
Content
Content
Content
Content
Content
Content
Ni Content
Ni Content
Electronics and electroplating applications
Method 066
Method
066
Version
Ni in Chem. Ni-Electrolyte
13-Sep-1991 13:39
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Instruktion
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set)[mV] . . . . .
Limits ∆V . . . . . .
∆V(min) . . . . . .
∆V(max) . . . . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
EQP range
. . . . . . .
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
Results last sample . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . 066
. . . . Ni in Chem. Ni-Electrolyte
. . . . 13-Sep-1991 13:39
. . . . 10mL NH3-Buffer, pH 10
. . . . + ca. 200 mg 1 : 500
. . . . Murexide trituration
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6
Stand 1
Fixed volume U
5.0
********
58.69
1
. . . . 60
. . . . 10
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EDTA
0.1
DP550
As installed
EQP
mL
1.0
DYN
8.0
Absolute
0.05
0.2
EQU
2.0
2.0
2.0
15.0
10.0
Yes
1000.0
0.0
20.0
Yes
1
Standard
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Ni Content
R1=Q*C1/U
C1=M/z
g/L
2
. . . . Printer
. . . . Yes
. . . . Yes
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R1
Yes
Yes
Yes
. . . . Printer
. . . . Yes
Literature
Remarks
• The buffer pH 10 is prepared by addition of
570 mL conc. NH3 and 70 g NH4Cl in a 1 L flask.
Deionised water is added to 1 L.
• The shape of the titration curve is somewhat affected by the concentration of the indicator. The
results, however, do not differ significantly (tested
range: 25-500 mg 1:500 murexide : NaCl trituration
pe sample).
• The results are given in g/L using the molar mass
M.
M(Ni) =
58.69 g/mol
M(NiCl2) = 129.6 g/mol
M(NiCl2•6H2O) = 237.7 g/mol.
• Nickel ions forms a yellow complex with murexide
in alkaline solution:
Ni 2+ + Murexide - = Ni-Murexide+
By adding EDTA, Ni forms a more stable complex
with EDTA:
Ni-Murexide+ + EDTA 4- = Ni-EDTA2-+ MurexideAt the equivalence point, all Ni ions have been
complexed by EDTA and murexide is free in the
alkaline solution. There is a colour change from
yellow to blue-violet.
• Nickel content of different baths:
Bath
n
Content / g/L
srel / %
LR-6/A
LR-37K
LR-200
ALT/IC
NM/a-1
IG/3-6
5
6
6
5
6
6
5.65
5.67
5.74
5.38
5.36
6.41
0.254
0.253
0.211
0.128
0.206
0.219
E-V curve
1. METTLER DL40RC Applications No. 107, 307.
2. METTLER DL25 Application No. 30
3. METTLER Applications No. M065 and M067
Disposal
Nickel solutions: special waste
Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77.
Author:
Electronics and electroplating applications
Kees Mooibroek
METTLER TOLEDO DL5x and DL7x Titrators Page 17/100
METTLER TOLEDO
M067
Electroless nickel bath: Determination of sodium orthophosphite
Sample:
Electroless nickel bath
0.5 mL
Substance:
Standard:
Instruments: METTLER TOLEDO DL70
Matrix Printer Epson LX800
with serial interface 8148
Sodium orthophosphite, Na2HPO3
M = 125.96 g/mol, z = 2
Preparation: - 20 mL 5% NaHCO3 solution
- 20 mL Iodine solution
c(1/2 I2) = 0.1 mol/L
- Oxidation reaction time in the
dark: 30 min.
Titrant 1:
Titrant 2:
Titrant 3:
Results:
For Na2S2O3 : Potassium iodate
Method:
067
Accessories: Titration beakers ME-23828
(brown glasses)
Two additional drives DV90
Two additional burettes DV1020
Iodine, c(1/2 I2) = 0.1 mol/L
Acetic acic, c(CH3COOH) = 2 mol/L
Sodium thiosulphate,
c(Na2S2O3) = 0.1 mol/L
Indication:
067 Orthophosphite in Chem. Ni
21-Nov-1991 12:44
SW Version 2.0
measured
Titrator
User
DM140-SC at Sensor 2
21-Nov-1991
P 5
KM
17:23
RESULTS
No
Identification
Volume
1/1
Chem.Ni
28/10B
0.5
mL
1/2
Chem.Ni
28/10B
0.5
mL
1/3
Chem.Ni
28/10B
0.5
mL
1/4
Chem.Ni
28/10B
0.5
mL
1/5
Chem.Ni
28/10B
0.5
mL
1/6
Chem.Ni
28/10B
0.5
mL
1/7
Chem.Ni
28/10B
0.5
mL
1/8
Chem.Ni
28/10B
0.5
mL
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
Results
n
x
s
srel
=
=
=
=
190.03
156.87
123.71
189.67
156.57
123.47
189.82
156.69
123.57
190.05
156.88
123.71
189.98
156.83
123.67
189.87
156.73
123.60
189.48
156.41
123.35
189.95
156.80
123.65
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
Na2HPO3
NaH2PO3
H3PO3
8
189.86
0.196
0.103
g/L
g/L
%
Na2HPO3
Na2HPO3
STATISTICS
Number results
Mean value
R2
n = 8
x = 156.72
g/L
NaH2PO3
STATISTICS
Number results
Mean value
R3
n = 8
x = 123.59
g/L
NaH2PO3
Page 18/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method 067
Method
067
Version
Orthophosphite in Chem.Ni
21-Nov-1991 12:44
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Dispense
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set)[mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
∆V(max) [%buVol]. .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
EQP range
. . . . . . .
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
Condition . . . . . . . . .
Condition . . . . . . . .
Record
Output unit . . . . . . . .
Results last sample . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . 067
. . . . Orthophosphite in Chem.Ni
. . . . 21-Nov-1991 12:44
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8
Stand 1
Fixed volume U
0.5
********
0.0
2
. . . . Acetic acid
. . . . 2
. . . . 20.0
. . . . 40
. . . . 20
Remarks
Electroless nickel bath
• Orthophosphite affects the behaviour of the bath.
The bath must be replaced as soon as a specific
concentration is reached.
Sample preparation (Method 067)
1) Add 20 mL 5% NaHCO3 to the sample.
2) 20 mL iodine c(1/2 I2) = 0.1 mol/L are dispensed
using the auxiliary function "Dosing" of the titrator. Cover the beaker to prevent loss of iodine.
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Na2S2O3
0.1
DM140-SC
mV
EQP
mL
0.0
DYN
8.0
Relative
0.5
2.5
EQU
1.0
3.0
3.0
30.0
150.0
Yes
1000.0
-1000.0
30.0
Yes
1
Standard
3) This oxidation is carried out at room temperature
in the dark during 30 minutes :
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Na2HPO3
R1=(H3-Q1)*C1/U
C1=125.9589/z
g/L
2
• The iodine excess is then titrated with method
067.
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NaH2PO3
R2=(H3-Q1)*C2/U
C2=103.9768/z
g/L
2
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H3PO3
R3=(H3-Q1)*C3/U
C3=81.9947/z
g/L
2
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CHECK CONCENTRATION
OF PHOSPHITE
Yes
R2>200
. . . . Printer
. . . . Yes
. . . . Yes
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R1
Yes
Yes
Yes
I2 + HPO32- + 3 OH - = 2I- + PO43- + 2 H2O
Procedure
• The orthophosphite concentration is determined by
an iodometric back titration.
• The iodine concentration is determined by a similar
method as 067. The result (mmol) is stored as auxiliary value H3 and used for the back-titration.
• The sample is acidified with 20 mL 2 mol/L acetic
acid immediately before titration.
• If the orthophosphite concentration exceeds the
limit of 200 g/L an instruction is displayed.
Nickel content of different baths
Bath
n
Content/ g/L
srel/%
28/10 A
28/10 B
3
8
189.00
189.66
0.158
0.103
Disposal
Nickel solutions: special waste
E-V curve
. . . . R2
. . . . Yes
. . . . R3
. . . . Yes
. . . . Printer
. . . . Yes
Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77.
Author:
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 19/100
Kees Mooibroek
METTLER TOLEDO
M151
Determination of acetic, phosphoric and nitric acid in a mixture
Sample:
Acid mixture
1 mL
Substance:
Acetic acid HAc
Phosphoric acid H3PO4
Nitric acid, HNO3
Instruments: METTLER TOLEDO DL58
METTLER TOLEDO ST20A
Printer EPSON SC600
Method:
Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
Preparation: 50 mL deion. water
Indication:
Titrant:
Sodium hydroxide, NaOH
c(NaOH) = 0.1 mol/L
Standard:
Potassium hydrogen phtalate
Results:
METTLER TOLEDO DL58
Method
Measured
User
Mix
Titrator
V2.0
DG111-SC
MTCS
ANA MS
Application Lab
Mix
HAc+HNO3+H3PO4
17-Mar-1999 16:20
Li Pei
16-Mar-1999
17:18
ALL RESULTS
No.
ID
Sample size and results
1
Mix. Acid
2
Mix. Acid
3
Mix. Acid
1.0
R1 = 0.9689
R2 = 0.9894
R3 = 0.4461
1.0
R1 = 0.9574
R2 = 0.9855
R3 = 0.4439
1.0
R1 = 0.9530
R2 = 0.9835
R3 = 0.4387
mL
mol/L
mol/L
mol/L
mL
mol/L
mol/L
mol/L
mL
mol/L
mol/L
mol/L
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
HNO3 content
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
3
0.9598 mol/L
0.00824 mol/L
0.859
%
HAc content
HAc content
STATISTICS
Number results
R2
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
3
0.9862 mol/L
0.00300 mol/L
0.304
%
H3PO4 content
H3PO4 content
STATISTICS
Number results
R3
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
3
0.4429 mol/L
0.00384 mol/L
0.867
%
HNO3 content
HNO3 content
Page 20/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
Mix
Version
Remarks
HAc+HNO3+H3PO4
16-Mar-1999 17:18
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Pump . . . . . . . . . . .
Solvent . . . . . . . .
Volume [mL] . . . . . .
Stir . . . . . . . . . .
Pump . . . . . . . . . . .
Rinse . . . . . . . . . . .
Solvent . . . . . . . .
Volume [mL] . . . . . .
Conditioning . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . Mix
. . . HAc+HNO3+H3PO4
. . . 21-Nov-1991 12:44
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Mix. Acid
Fixed volume
1.0
100
2
ST20A
Yes
H 2O
50.0
No
No
Yes
H 2O
10.0
No
Manual
. . . 50
. . . 10
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NaOH
0.1
DG111
mV
to volume
2.5
0
Dynamic
8.0
0.02
0.2
Equilibrium controlled
1.0
1.0
2.0
10.0
.
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17.0
No
No
None
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40.0
No
No
Yes
3
No
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Standard
No
No
No
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.
R1=Q2*C1/m
C1=1/z
4
mol/L
HAc content
Yes
.
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.
R2=Q3*C2/m
C2=1/z
4
mol/L
H3PO4 content
Yes
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.
R3=(Q1-Q3)*C3/m
C3=1/z
4
mol/L
HNO3 content
Yes
.
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Printer
No
Yes
No
No
No
No
No
No
No
No
No
No
Electronics and electroplating applications
• This titration procedure includes four steps:
1. HNO3 =
H+ + NO32. H3PO4 =
H+ + H2PO43. HAc
=
H+ + Ac+
4. H2PO4 =
H + HPO42Due to the little difference between the pKavalue of HNO3 (pKa=approx. -1.3) and H3PO4
(pKa1=2.12), the first two steps can not be
distinguished. Therefore only three potential
jumps can be seen on the titration curve.
• A sample changer ST20A is used in this method
for a fully automatic procedure. The method
can be easily modified for manual operation:
enter "Stand 1" as titration stand in the function
SAMPLE.
Disposal
Neutralization with hydrochloric acid.
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
E-V curve
Author:
Li Pei
METTLER TOLEDO DL5x and DL7x Titrators Page 21/100
METTLER TOLEDO
M152
Nitric, acetic and phosphoric acid mixture: large excess of phosphoric acid
Sample:
Acid cleaner
0.5 g
Substance:
Nitric acid, HNO3 ; Acetic acid
HAc; Phosphoric acid H3PO4
Instruments: METTLER TOLEDO DL58
METTLER TOLEDO ST20A
Printer EPSON SC600
HNO3 : HAc : H3PO4 = approx. 1 : 4 : 23
Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
Preparation: 50 mL deion. water
(dispensed by pump)
Sodium hydroxide, NaOH
c(NaOH) = 1 mol/L
Standard:
Potassium hydrogen phtalate
Method
Measured
User
DG111-SC
Indication:
Titrant:
Results:
2.2
Method:
2.2
EQP Titration
07/17/2000
14:48
YY
07/17/2000
13:59
ALL RESULTS
No.
1
2
3
4
5
6
ID
Sample size and results
0.5102
R1 = 3.0723
R2 = 12.2359
R3 = 70.9786
0.5199
R1 = 3.0858
R2 = 12.0854
R3 = 70.8494
0.518
R1 = 2.9778
R2 = 11.9648
R3 = 70.9050
0.5373
R1 = 3.1480
R2 = 11.8686
R3 = 70.7380
0.5176
R1 = 3.0152
R2 = 11.7205
R3 = 70.7452
0.5078
R1 = 3.0452
R2 = 11.6033
R3 = 70.6551
g
%
%
%
g
%
%
%
g
%
%
%
g
%
%
%
g
%
%
%
g
%
%
%
HNO3 content
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
HNO3 content
HAc content
H3PO4 content
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
6
3.0574 %
0.05917 %
1.935
%
HNO3 content
HNO3 content
STATISTICS
Number results
R2
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
6
11.9131 %
0.23308 %
1.957
%
HAc content
HAc content
STATISTICS
Number results
R3
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
6
70.8119 %
0.12031 %
0.170
%
H3PO4 content
H3PO4 content
Page 22/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
2.2
Version
Remarks
EQP Titration
07/17/2000
13:59
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Pump . . . . . . . . . . .
Solvent . . . . . . . .
Volume [mL] . . . . . .
Stir . . . . . . . . . .
Pump . . . . . . . . . . .
Rinse . . . . . . . . . . .
Solvent . . . . . . . .
Volume [mL] . . . . . .
Conditioning . . . . . . .
Time [s] . . . . . . . .
Interval . . . . . . . .
Rinse . . . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
Potential [mV, pH,..] .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Pot. 1 [mV, pH,..] . . .
Potential 2 . . . . . . . .
Pot. 2 [mV, pH,..] . . .
Stop for reevaluation . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . 2.2
. . . EQP Titration
. . . 07/17/2000
13:59
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Weight
0.4
0.6
98
1
ST20A
Yes
H 2O
50.0
No
No
Yes
H 2O
20.0
Yes
20
1
No
Manual
. . . 50
. . . 10
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NaOH
1.0
DG111
pH
to volume
3
10
Dynamic
10.0
0.005
0.2
Equilibrium controlled
0.3
2.0
5.0
52.0
.
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6.0
No
No
None
.
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12.0
Yes
10.5
No
Yes
1
Yes
.
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Standard
Yes
3.75
Yes
5.5
No
.
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.
R=(QP1-(Q-QP2))*C/m
C=63.01/(10*z)
4
%
HNO3 content
Yes
.
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.
R2=(QP2-QP1)*C2/m
C2=60.05/(10*z)
4
%
HAc content
Yes
.
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.
R3=(Q-QP2)*C3/m
C3=M/(10*z)
4
%
H3PO4 content
Yes
.
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.
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Electronics and electroplating applications
• This titration procedure includes four steps:
=
H+ + NO31. HNO3
2. H3PO4
=
H+ + H2PO43. HAc
=
H+ + Ac4. H2PO4=
H+ + HPO42Due to the little difference between the pKa-value
of HNO3 and H3PO4 ,the first two steps can not be
distinguished. Therefore only three potential jumps
can be seen on the titration curve.
• The two potential jumps are evaluated at potential
values of pH 3.75 and 5.5 (see evaluation). These
values are determined by a trial titration. From the
table of measured values the pH values corresponding to the potential jumps can be easily determined.
The values are then used for sample analysis.
Note that these values depend on the concentration
of the sample and on sample preparation. Thus, it
is necessary to first determine the potential values
for any other mixture.
Disposal
Neutralization with hydrochloric acid.
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
E-V curve
Author:
Lin Yau Yeng (YY)
METTLER TOLEDO DL5x and DL7x Titrators Page 23/100
METTLER TOLEDO
M153
Nitric, acetic and phosphoric acid mixture: concentrations below 0.3%
Sample:
Acid cleaner
10 mL
Instruments: METTLER TOLEDO DL70ES
Printer EPSON SC600
Substance:
Nitric acid, HNO3, 0.1 %
Acetic acid HAc, 0.1%
Phosphoric acid H3PO4, 0.25%
Method:
Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
HNO3 : HAc : H3PO4 = approx. 1 : 1 : 2
Titrant:
Sodium hydroxide, NaOH
c(NaOH) = 0.1 mol/L
Standard:
Potassium hydrogen phtalate
METTLER DL70ES
Method
User
Measured
DG111-SC
Indication:
Preparation: 40 mL deion. water
Results:
Y021
Titrator
V3.1
titration introduction 1998
market support analytical
Y021 Mixed Acids-HNO3,H3PO4,HAc Apr/23/1999
YY
Apr/23/1999
1:36 pm
10:34 am
RESULTS
No
ID1
ID2
1/1
Sample amount and results
1/2
10.0
R1 = 0.0935
R2 = 0.1160
R3 = 0.2517
10.0
R1 = 0.0925
R2 = 0.1179
R3 = 0.2508
10.0
R1 = 0.0959
R2 = 0.1164
R3 = 0.2501
1/3
mL
%
%
%
mL
%
%
%
mL
%
%
%
Fixed volume U
Nitric Acid
Acetic Acid
Phosphoric
Fixed volume U
Nitric Acid
Acetic Acid
Phosphoric
Fixed volume U
Nitric Acid
Acetic Acid
Phosphoric
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
3
0.0940
%
0.001711 %
1.821
%
Nitric Acid
Nitric Acid
STATISTICS
Number results
R2
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
3
0.1168
%
0.001026 %
0.878
%
Acetic Acid
Acetic Acid
STATISTICS
Number results
R3
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
=
=
=
=
3
0.2509
%
0.000804 %
0.321
%
Phosphoric
Phosphoric
Page 24/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
Y021
Version
Remarks
Mixed Acids-HNO3,H3PO4,HAc
Apr/23/1999 10:34 am
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [mL] . . .
∆V(min) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Record
Output unit . . . . . . . .
All results . . . . . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
∆E/∆V - V curve . . . . . .
. . . . Y021
. . . . Mixed Acids-HNO3,H3PO4,HAc
. . . . Apr/23/1999 10:34 am
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3
Stand 1
Fixed volume U
10.0
98
1
Manual
. . . . 50
. . . . 10
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NaOH
0.1
DG111-SC
mV
EQP
mL
0
DYN
8.0
Absolute
0.05
0.2
EQU
0.2
1.0
3.0
30.0
40.0
10.0
Yes
4
Standard
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Nitric Acid
R=(Q-Q(EPOT<-100))*C/U
C=63/(10*z)
%
4
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Acetic Acid
R2=Q(100>EPOT>-80)*C2
C=60/(U*10*z)
%
4
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Phosphoric
R3=Q(EPOT<-100)*C3/U
C=M*3/(10*3)
%
4
• This titration procedure includes four steps:
=
H+ + NO31. HNO3
2. H3PO4
=
H+ + H2PO43. HAc
=
H+ + Ac4. H2PO4
=
H+ + HPO42Due to the little difference between the pKa-value
of HNO3 and H3PO4 , the first two steps can not be
distinguished. Therefore only three potential jumps
can be seen on the titration curve.
• The potential jumps are evaluated by means of
control ranges. To set the optimum values for the
control ranges, a trial titration must be first performed. From the table of measured values the appropriate control ranges can be selected and stored
in the method.
Note that these values depends on the concentration
of the sample and on sample preparation. Thus, it
is necessary to first determine these values for any
other acid mixture.
Disposal
Neutralization with hydrochloric acid.
E-V curve
. . . . R1
. . . . Yes
. . . . Yes
. . . . R2
. . . . Yes
. . . . Yes
. . . . R3
. . . . Yes
. . . . Yes
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Printer
Yes
Yes
Yes
Yes
Other titrators
DL50 Graphix, DL53/DL55, DL77.
Electronics and electroplating applications
Author:
Lin Yau Yeng (YY)
METTLER TOLEDO DL5x and DL7x Titrators Page 25/100
METTLER TOLEDO
M154
Sample:
Substance:
Simultaneous titration of HCl, CH3COOH, and NH4Cl
Standard:
3 mL acid mixture
(1 mL of each acid)
Hydrochloric acid HCl, 0.1 mol/L
Acetic acid HAc, 0.1 mol/L
Ammonium chloride, NH4Cl,
0.1 mol/L
Results:
Sodium hydroxide, NaOH
c(NaOH) = 0.1 mol/L
Sample
Instruments: METTLER TOLEDO DL77
Printer EPSON SC600
METTLER TOLEDO ST20A
WS2
Method:
Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
Preparation: 40 mL deion. water
Titrant:
Potassium hydrogen phtalate
Indication:
DG111-SC
DG111-1
DG111-2
DG111-3
(mg HCl)
(mg HCl)
(mg HCl)
1
2
3
4
5
6
0.364
0.37
0.373
0.373
0.378
0.372
0.366
0.365
0.365
0.367
0.374
0.367
0.366
0.367
0.373
0.375
0.371
0.37
x
s
srel
0.372
0.00459
1.235%
0.367
0.00339
0.922%
0.370
0.00344
0.930%
Sample
DG111-1
DG111-2
DG111-3
(mg CH3COOH)
(mg CH3COOH)
(mg CH3COOH)
1
2
3
4
5
6
0.599
0.589
0.577
0.591
0.584
0.593
0.599
0.599
0.6
0.598
0.589
0.597
0.602
0.602
0.592
0.589
0.594
0.594
x
s
srel
0.589
0.00760
1.291%
0.597
0.00405
0.678%
0.596
0.00536
0.900%
Sample
DG111-1
DG111-2
DG111-3
(mg NH4Cl)
(mg NH4Cl)
(mg NH4Cl)
1
2
3
4
5
6
0.553
0.547
0.575
0.558
0.544
0.553
0.547
0.558
0.563
0.555
0.55
0.552
0.55
0.565
0.551
0.56
0.547
0.544
x
s
srel
0.555
0.01097
1.977%
0.554
0.00578
1.042%
0.553
0.00804
1.453%
Page 26/100 METTLER TOLEDO DL5x and DL7x Titrators
Theoretical
content
(mg HCl)
0.365
Theoretical
content
(mg CH3COOH)
0.6
Theoretical
content
(mg NH4Cl)
0.535
Electronics and electroplating applications
Remarks
Method
Method
WS2
Version
HCl/HOAc/NH4Cl
Sep/10/1999
9:49 am
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [mL] . . . .
Upper limit [mL] . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Titrant addition . . . .
dE(set) [mV] . . . . .
Limits dV . . . . . .
dV(min) [mL] . . .
dV(max) [mL] . . .
Measure mode . . . . . .
dE [mV] . . . . . . .
dt [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Evaluation procedure . .
Stop for reevaluation . .
Condition . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
Results last sample . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
dE/dV - V curve . . . . . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . WS2
. . . . HCl/HOAc/NH4Cl
. . . . Sep/10/1999
9:49 am
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6
ST20 1
Volume U
0.5
2.5
Serie2
36.46
1
Manual
. . . . 50
. . . . 20
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NaOH
0.1
DG111-SC
As installed
EQP
DYN
8.0
Absolute
0.03
0.1
EQU
0.5
1.0
3.0
30.0
2.2
4.0
Standard
Yes
neq=0
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HCl
R1=Q1*C1/U
C1=M/(10*z)
mg/L
3
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HOAc
R2=Q2*C2/U
C2=60.0/(10*z)
mg/L
3
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NH4Cl
R3=Q3*C3/U
C3=53.49/(10*z)
mg/L
3
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Printer
Yes
Yes
Yes
Yes
• A mixture of three different acids (hydrochloric
acid, acetic acid and ammonium chloride) with
clear different acid dissociation constant (pKa
= -10, 4.75, and 9.25, respectively) is titrated
with 0.1 M NaOH.
• The mixture is prepared by adding 1 mL 0.1
mol/L of each acid soution into the titration
beaker. The mixture is diluted with 40 mL
deionized water before titration.
• Reactions:
Dominating reaction in the pH-range 2.8-5.0:
HCl + NaOH
=
Na + + Cl - + H 2 O
Dominating reaction in the pH-range 5.0-9.0:
CH3COOH + NaOH = CH3COO- + Na+ + H2O
Dominating reaction in the pH-range
9.0-11.5:
NH4Cl + NaOH = Na+ + Cl- + NH3 + H2O
Disposal:
---
. . . . H2O
. . . . 20.0
. . . . R1
. . . . Yes
. . . . Yes
. . . . R2
. . . . Yes
. . . . Yes
. . . . R3
. . . . Yes
. . . . Yes
. . . . Printer
. . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL70ES.
Electronics and electroplating applications
Authors: H.-J. Muhr, E. Renaud Gueletti, J.Zarske
METTLER TOLEDO DL5x and DL7x Titrators Page 27/100
METTLER TOLEDO
M155
Polishing bath: determination of sulfuric and phosphoric acid
Sample:
1 mL polishing bath
(density: 1.981 g/cm3)
Substance:
Sulfuric acid
Phosphoric acid
Instruments: METTLER TOLEDO DL67
Printer EPSON LX400
METTLER TOLEDO ST20A
Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
Preparation: - 1:10 dilution
- 50 mL deion. water
Indication:
Titrant:
Sodium hydroxide, NaOH
c(NaOH) = 0.5 mol/L
Standard:
Potassium hydrogen phtalate
Results:
METTLER DL67
Method
User
Measured
hpo4
Method:
Titrator
DG111-SC
V3.1
hpo4 H2SO4+H3PO4 in Polstar
YY
21-02-1994 10:42
21-02-1994
10:15
RESULTS
No
ID1
ID2
1/1
Sample amount and results
1/2
0.1781
R1 = 49.06
R2 = 29.04
0.1781
R1 = 48.89
R2 = 29.24
0.1781
R1 = 49.01
R2 = 29.38
1/3
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
Page 28/100 METTLER TOLEDO DL5x and DL7x Titrators
=
=
=
=
g
%
%
g
%
%
g
%
%
Weight m
Phosphoric
Sulfuric
Weight m
Phosphoric
Sulfuric
Weight m
Phosphoric
Sulfuric
3
48.99
%
0.088515 %
0.181
%
Phosphoric
Phosphoric
Electronics and electroplating applications
Remarks
Method
Method
hpo4
Version
H2SO4+H3PO4 in Polstar
21-02-1994
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [g] . . . . .
Upper limit [mL] . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1
. . . .
Volumen [mL]
. . . .
Titrant addition . . . .
dE(set) [mV] . . . . .
Limits dV . . . . . .
dV(min) [mL] . . .
dV(max) [mL] . . .
Measure mode . . . . . .
dE [mV] . . . . . . .
dt [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Record
Output unit . . . . . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
10:15
. . . . WS2
. . . . H2SO4+H3PO4 in Polstar
. . . . 21-02-1994
10:15
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3
ST20 1
Weight m
0.0
2.0
98
1
Manual
. . . . 50
. . . . 10
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NaOH
0.5
DG111-SC
mV
EQP
mL
0.1
DYN
8.0
Absolute
0.05
0.5
EQU
0.5
1.0
2.0
20.0
50.0
30.0
Yes
1
Standard
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Phosphoric
R1=Q2*C1/m
C1=98/(10*z)
%
2
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Sulfuric
R2=((Q1*2)-(Q1+Q2))*C2
C2=98/(10*z)
%
2
. . . . R1
. . . . Yes
. . . . Yes
. . . . Printer
. . . . Yes
. . . . Yes
. . . . H2O
. . . . 20.0
• Sample preparation:
1 mL polishing bath is first diluted with water
(1:10). Again, 1 mL of the diluted solution is added
into the titration beaker together with 50 mL deionized water.
• Sulfuric and phosphoric acid can dissociate two
protons H+ (sulfuric acid, H2SO4) and three protons
H+ (phosphoric acid, H3PO4), respectively.
The dissociation constants pKa of H2SO4 are:
pKa1 = approx. -3,
pKa2 = 1.92.
Sulfuric acid is a strong acid that dissociates completely in water.
The dissociation constants pKa of H3PO4 are:
pKa1 = 2.12
pKa2 = 7.21
pKa3 = 12.67
In aqueous solution only the first two dissociation
steps of phosphoric acid can be monitored, while
the third one is too weak .
Based on the pK-values of the two acids in water,
the following reactions can be given for the two
EQPs found during titration:
1st EQP:
H2SO4 + NaOH
HSO4- + NaOH
H3PO4 + NaOH
=
=
=
Na+ + HSO4- + H2O
Na+ + SO42- + H2O
H2PO4- + Na+ + H2O
2nd EQP:
H2PO4- + NaOH
=
HPO42- + Na+ + H2O
Disposal
Neutralization with hydrochloric acid.
E-V curve
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Electronics and electroplating applications
Authors: Application Laboratory MT-Germany
METTLER TOLEDO DL5x and DL7x Titrators Page 29/100
METTLER TOLEDO
M156
Determination of boric acid in acidic mixtures of HCl and HF
Sample:
Boric acid solution, 5 mL
Substance:
Hydrochloric acid, HCl
Hydrofluoric acid, HF
Boric acid, H3BO3
Instruments: METTLER TOLEDO DL70
Printer EPSON FX850
with serial interface
Preparation: - 30 mL deion. water
- 20 mL Mannitol solution
(c(Mannitol) = approx. 200g/L)
Titrant:
Sodium hydroxide, NaOH
c(NaOH) = 0.1 mol/L
Standard:
Potassium hydrogen phtalate
Results:
METTLER DL70
A001
Method:
Accessories: Titration beakers ME-101974
Additional burette drive DV90
Additional burette DV1020
DG115-SC
Indication:
Titrator
A001 Borsäure
14-Nov-1989 12:28
SW Version 1.2
measured
Titrator
User
14-Nov-1989
12:44
****
RESULTS
No
1/1
Ientification
Weight
0.0
Page 30/100 METTLER TOLEDO DL5x and DL7x Titrators
Result
g
5.179
9.245
mL
mL
mL HCl/HF
mL Brsaeure
Electronics and electroplating applications
Remarks
Method
Method
A001
Version
Borsäure
14-Nov-1989
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [mL] . . . .
Upper limit [mL] . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing
. . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
∆V(min) [mL] . . . . .
∆V(max) [mL] . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Endpoint mode . . . . . .
Potential [mV,pH,...].
Tendency . . . . . . . .
Maximum volume [mL] . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
All results . . . . . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
Dispense
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volumen [mL]
. . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [mL]. . . .
∆V(max) [mL]. . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
All results . . . . . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
12:28
. . . . A001
. . . . Borsäure
. . . . 14-Nov-1989
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12:28
1
Stand 1
Weight m
0.05
0.15
61.83
1
. . . . 50
. . . . 10
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NaOH
0.1
DG115-SC
mV
EP
mL
1.0
Dynamic
8.0
0.02
0.1
0.5
0.5
2.0
20.0
EPA
0.0
Negative
10.0
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mL HCl/HF
R=VEQ[1]
mL
3
• Sample preparation:
200g mannitol are dissolved in 1 L volumetric flask
with deion. water.
Boric acid can not be titrated directly in electroplating solution since it is a weak acid. To allow
titration, mannitol is added to the sample. Mannitol
forms a complex with boric acid giving in a medium
strong acidic compounds.
• A sample changer ST20A can be used in this method
for a fully automatic procedure. The method can
be easily modified for automatic operation: enter
"ST20 1" as titration stand in the function SAMPLE.
• CAUTION: Hydrofluoric acid is poisonous! Work
in a fume hood, wear safety goggles and gloves.
Disposal
Neutralization with hydrochloric acid.
E-V curve:
Titration of HCl/HF
. . . . Yes
. . . . Yes
. . . . Yes
. . . . Mannitol
. . . . 0.0
. . . . 20.0
. . . . 50
. . . . 60
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NaOH
0.1
DG115-SC
mV
EQP
mL
1.0
DYN
8.0
Absolute
0.02
0.2
EQU
1.0
1.0
3.0
30.0
20.0
10.0
Standard
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mL Brsaeure
R2=VEQ[2]
Titration of boric acid
mL
3
. . . . Yes
. . . . Yes
. . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Electronics and electroplating applications
Author: Dieter Rehwald
METTLER TOLEDO DL5x and DL7x Titrators Page 31/100
Note:
Determination of nitric and hydrofluoric acid in stainless steel polishing bath
Sample:
1st titration: 0.5 g polishing bath
2nd titration: 1 g polishing bath
Titrant:
Potassium hydroxide, KOH
c(NaOH) = 1.0 mol/L
Substance:
Nitric acid, HNO3
Hydrofluoric acid, HF
Standard:
Potassium hydrogen phtalate
Preparation: 1 titration function:
1.1 Weigh 0.5 g of acid sample.
1.2 Take 10 mL potassium fluoride solution (KF, e.g. 10%)
and dilute it to 50 mL with
deionized water.
1.3 Add the diluted KF solution
to the sample.
2nd titration function:
2.1 Weigh 0.5 g of acid sample.
2.2 Add 50 mL acetone
2.3 Add 4 g of sodium sulphate
st
Instruments: METTLER TOLEDO DL70ES
Printer EPSON FX850
with serial interface
Method:
HF1
(This method consists of two
titration functions).
Accessories: Titration beakers ME-101974
Indication:
InLab429
Remarks
• Principle of the method:
This method allows the determination of the nitric and hydrofluoric acid content in stainless steel
polishing bath. It consists of two sample and two titration functions.
For a complete analysis, two samples are needed. With the first sample, the total acid strength of
the bath is determined by titration with KOH (first titration function), while the second sample is
used for the determination of the HNO3-content (second titration). The difference of these results
determines the HF-content.
• Total acid strength:
Steel mainly contains iron, chromium and nickel and other metal ions. These metal ions can affect
the analysis, e.g. they can form hydroxide complexes due to the titrant addition of KOH.
Therefore, an excess of potassium fluoride solution is added to avoid interference. In fact, fluoride
ions form complexes with metal ions (e.g. Al), and thus, it can mask them.
• HNO3-content:
Hydrofluoric acid (HF) and nitric acid (HNO3) are both strong acids in aqueous solution (dissociation
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
Method
HF1
Version
HF and HNO3 Content
Dec/03/1998
11:25 am
Title
Method ID . . . . . . . . . . . .
Title . . . . . . . . . . . . . .
Date/time . . . . . . . . . . . .
Sample
Number samples . . . . . . . . . .
Titration stand . . . . . . . . .
Entry type . . . . . . . . . . . .
Lower limit [mL] . . . . . . .
Upper limit [mL] . . . . . . .
ID1 . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . .
Equivalent number z . . . . . . .
Temperature sensor . . . . . . . .
Stir
Speed [%] . . . . . . . . . . . .
Time [s] . . . . . . . . . . . . .
Titration
Titrant . . . . . . . . . . . . .
Concentration [mol/L] . . . . . .
Sensor . . . . . . . . . . . . . .
Unit of meas. . . . . . . . . . .
Titration mode . . . . . . . . . .
Predispensing 1 . . . . . . . .
Volume [mL] . . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . . .
Limits ∆V . . . . . . . . .
∆V(min) [mL] . . . . . .
∆V(max) [mL] . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . . .
t(min) [s] . . . . . . . . .
t(max) [s] . . . . . . . . .
Threshold . . . . . . . . . . .
Maximum volume [mL] . . . . . .
Termination after n EQPs . . .
n = . . . . . . . . . . . .
Termination at slope . . . . .
Slope [mV,pH,.../mL] . . . .
Combined termn criteria . . . .
Evaluation procedure . . . . .
Steepest jump only . . . . . .
Stop for reevaluation . . . . .
Condition . . . . . . . . .
Calculation
Result name . . . . . . . . . . .
Formula . . . . . . . . . . . . .
Constant . . . . . . . . . . . . .
Result unit . . . . . . . . . . .
Decimal places . . . . . . . . . .
Record
Output unit . . . . . . . . . . .
Result last sample . . . . . . . .
Table of values . . . . . . . . .
E - V curve . . . . . . . . . . .
Statistics
Ri (i=index) . . . . . . . . . . .
Standard deviation s . . . . . . .
Rel. standard deviation srel . . .
Sample
Number samples . . . . . . . . . .
Titration stand . . . . . . . . .
Entry type . . . . . . . . . . . .
Lower limit [mL] . . . . . . .
Upper limit [mL] . . . . . . .
ID1 . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . .
Equivalent number z . . . . . . .
Temperature sensor . . . . . . . .
Instruction
Attach sample with sodium sulphate
added and acetone as a solvent
Stir
Speed [%] . . . . . . . . . . . .
Time [s] . . . . . . . . . . . . .
. HF1
. HF and HNO3 Content
. Dec/03/1998
11:25 am
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3
Stand 1
Weight m
0.0
1.0
HNO3
63.0129
1
Manual
. 50
. 30
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KOH
1.0
InLab 429
mV
EQP
mL
1.0
DYN
8.0
Absolute
0.02
0.5
EQU
0.5
1.0
3.0
30.0
100.0
20.0
Yes
1
Yes
50.0
Yes
Standard
Yes
Yes
neq=0
.
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.
Total acid
R=Q*C/m
C=1/z
mmol/g
4
.
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Printer
Yes
Yes
Yes
. R1
. Yes
. Yes
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3
Stand 1
Weight m
0.0
1.0
HF
20.0063
1
Manual
. 50
. 60
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [mL] . . .
∆V(max) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Termination at slope . .
Slope [mV,pH,.../mL] .
Combined termn criteria .
Evaluation procedure . .
Steepest jump only . . .
Stop for reevaluation . .
Condition . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
Result last sample . . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
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KOH
1.0
InLab 429
mV
EQP
mL
1.0
DYN
8.0
Absolute
0.02
0.5
EQU
0.5
1.0
3.0
30.0
100.0
20.0
Yes
1
Yes
50.0
Yes
Standard
Yes
Yes
neq=0
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HNO3 Content
R2=Q[2]*C2/m
C2=1/z
mmol/g
4
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Printer
Yes
Yes
Yes
. . . . R2
. . . . Yes
. . . . Yes
.
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.
HNO3 Content
R3=R2*C3/m
C3=63.0129/(10*z)
%
3
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.
HF Content
R4=(R1-R2)*C4
C4=20.0063/(10*z)
%
3
. . . . Printer
. . . . Yes
Remarks
• A sample changer ST20A can be used in this
method for a fully automatic procedure. The
method can be easily modified for automatic
operation: enter "ST20 1" as titration stand in
the function SAMPLE.
• CAUTION: HF is a very strong acid and it
etches glass. Wear gloves and safety goggles.
Disposal
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Electronics and electroplating applications
Neutralization with hydrochloric acid.
Author: Craig Gordon
METTLER TOLEDO DL5x and DL7x Titrators Page 33/100
METTLER TOLEDO
M157
Determination of hydrochloric and nitric acid
Sample:
Acid mixture, 1 g
Substance:
Nitric acid, HNO3 , appr. 25%
Hydrochloric acid, HCl , appr. 3%
Preparation: method jud3:
50 mL deion. water
method jud2:
1 mL 10% HNO3 in the sample
titrated with method jud3
Titrant 1:
Sodium hydroxide, NaOH
c(NaOH) = 1 mol/L
Titrant 2:
Silver nitrate, AgNO3
c(AgNO3) = 1 mol/L
Standard:
Results:
Instruments: METTLER TOLEDO DL58
Printer EPSON SC600
Accessories: Second burette drive DV90 Second burette DV1010
pH Option
Titration beakers ME-101974
Peristaltic pump ME-65241
Indication:
NaOH: Potassium hydrogen phthalate
AgNO3: Sodium chloride
Method
Measured
User
jud3:
Determination of total acid content.
jud2:
Determination of hydrochloric
and nitric acid content.
Methods:
DG111-SC
DM141-SC
jud3 Total acid cont (HCl+HNO3) 08/08/2000
08/08/2000
12:32
J. Maag
12:20
ALL RESULTS
No.
1
ID
Sample size and results
HCl/HNO3
1.011
R1 = 29.291
Method
Measured
User
g
%
jud2 EQP det. with AgNO3
08/08/2000
12:42
J. Maag
mmol H+
08/08/2000
12:21
ALL RESULTS
No.
1
ID
Sample size and results
HCl/HNO3
1.011
R1 = 29.291
R2 = 2.676
Page 34/100 METTLER TOLEDO DL5x and DL7x Titrators
g
%
%
HCl content
HNO3
Electronics and electroplating applications
Method jud3
Method
jud3
Version
Title
Method ID
Title
Method jud2
Total acid cont (HCl+HNO3)
08/08/2000 12:20
. . . . . . . . . . . . . jud3
. . . . . . . . . . . . . Total acid cont
(HCl+HNO3)
. . . . . . . . . . . . . 08/08/2000 12:20
Date/time
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Auxiliary value
ID . . . . . . . . . . . . . .
Constant . . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
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.
.
.
.
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.
.
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.
.
.
.
.
.
.
HCl/HNO3
Weight
0.02
2.0
100
1
Stand 1
Manual
. . . 50
. . . 10
.
.
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.
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.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
NaOH
1.0
DG111
pH
No
Dynamic
4.0
0.01
0.1
Equilibrium controlled
0.5
1.0
3.0
30.0
.
.
.
.
.
.
.
.
.
.
.
.
50.0
No
No
None
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=Q
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
3
mmol
H+
No
. . . Total acid
. . . H5=R
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
Printer
No
Yes
Yes
Yes
No
Yes
Yes
No
No
No
No
No
Remarks
1.
2.
3.
Method jud3: det. of total acid content.
Add 1 mL 10% HNO3 for chloride precipitation
Method jud2: determination of HCl by precipitation of chloride with AgNO3
4. Difference 1.-2. = content HNO3
Please note that both methods can be summarized in
a single method.
Electronics and electroplating applications
Method
jud2
Version
HCl det. with AgNO3
08/08/2000 12:49
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . jud2
. . . HCl det. with AgNO3
. . . 08/08/2000 12:49
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
HCl/HNO3
Weight
0.02
2.0
36.45
1
Stand 1
Manual
. . . 50
. . . 10
.
.
.
.
.
.
.
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.
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.
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.
.
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.
.
.
.
.
.
.
.
AgNO3
1.0
DM141
mV
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
1.0
3.0
30.0
.
.
.
.
.
.
.
.
.
.
.
.
1000.0
No
No
None
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=Q*C/m
C=M/(10*z)
3
%
HCl content
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R2=(H5-Q)*C2/m
C2=63.01/(10*z)
3
%
HNO3
Yes
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
.
.
.
.
.
.
.
Printer
No
Yes
Yes
Yes
No
Yes
Yes
No
No
No
No
No
Disposal
Filtration/Neutralization with sodium hydroxide.
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author:
Judy Maag
METTLER TOLEDO DL5x and DL7x Titrators Page 35/100
METTLER TOLEDO
M158
Determination of ammonia and hydrogen peroxide
Sample:
Alkaline mixture, 0.5-1 g
Substance:
Ammonia, NH3
Hydrogen peroxide, H2O2
Preparation: method amm1:
50 mL deion. water
method hydr1:
1 mL 10% HNO3 in the sample
titrated with method amm1
Titrant 1:
Sodium hydroxide, NaOH
c(NaOH) = 1 mol/L
Titrant 2:
Nitric acid, HNO3
c(HNO3) = 2 mol/L
Titrant 3:
Potassium permanganate, KMnO4
c(1/5 KMnO4) = 0.1 mol/L
Standard:
NaOH: Potassium hydrogen phthalate
HNO3: THAM (Tris)
KMnO4: sodium oxalate, Na2C2O4
Results:
Method
Measured
User
Instruments: METTLER TOLEDO DL58
Printer EPSON SC600
amm1:
Back titration of NH3
hydr1:
Redox titration of H2O2
Methods:
Accessories: Second burette drive DV90 Second burette DV1010
pH Option
Titration beakers ME-101974
Indication:
amm1 Back titration of NH3
08/11/2000
13:31
J. Maag
DG111-SC
DM140-SC
08/11/2000
13:29
ALL RESULTS
No.
1
ID
Sample size and results
NH3/H2O2
0.662
R1 = 3.484
Method
Measured
User
g
%
hydr1 H2O2 determination
08/11/2000
13:37
J. Maag
NH3 Content
08/11/2000
12:50
ALL RESULTS
No.
1
ID
Sample size and results
NH3/H2O2
0.662
R1 = 0.936
Page 36/100 METTLER TOLEDO DL5x and DL7x Titrators
g
%
H2O2 content
Electronics and electroplating applications
Method amm1
Method
amm1
Version
Method hydr1
Back titration of NH3
08/11/2000 13:29
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Dispense
Titrant . . . . . . . . . . .
Concentration [mol/L] . . . .
Volume [mL] . . . . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . amm1
. . . Back titration of NH3
. . . 08/11/2000 13:29
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
NH3/H2O2
Weight
0.02
2.0
17
1
Stand 1
Manual
. . . HNO3
. . . 2.0
. . . 4.5
. . . 50
. . . 10
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
NaOH
1.0
DG111
pH
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
1.0
3.0
30.0
.
.
.
.
.
.
.
.
.
.
.
.
100.0
No
No
Positive
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=(QDISP-Q)*C/m
C=M/(10*z)
3
%
NH3 Content
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Remarks
1.
2.
Method amm1: det. of NH3 by back titration.
Add 1 mL 10% HNO3 for peroxide determination
3. Method hydr1: determination of HCl by redox
titration with 1/5 KMnO4.
Please note that both methods can be resumed in a
Electronics and electroplating applications
Method
hydr1
Version
H2O2 determination
08/11/2000 12:50
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . hydr1
. . . H2O2 determination
. . . 08/11/2000 12:50
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
NH3/H2O2
Weight
0.02
2.0
34.02
1
Stand 1
Manual
. . . 50
. . . 10
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
1/5 KMnO4
0.1
DM140
mV
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
1.0
3.0
15.0
.
.
.
.
.
.
.
.
.
.
.
.
2000.0
No
No
Positive
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
8.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
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.
.
.
.
.
.
.
.
.
.
R=Q*C/m
C=M/(10*z)
3
%
H2O2 content
Yes
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
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.
Printer
No
Yes
Yes
Yes
No
Yes
Yes
No
No
No
No
No
Disposal
The sample has to be classified as special waste.
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author:
Judy Maag
METTLER TOLEDO DL5x and DL7x Titrators Page 37/100
METTLER TOLEDO
M159
Determination of hydrochloric acid and hydrogen peroxide
Sample:
Acid mixture, 0.5-1 g
Substance:
Hydrochloric acid, HCl
Hxdrogen peroxide, H2O2
Preparation: method hcl1:
50 mL deion. water
method hydr1:
1 mL 10% HNO3 in the sample
titrated with method hcl1
Titrant 1:
Sodium hydroxide, NaOH
c(NaOH) = 1 mol/L
Titrant 2:
Potassium permanganate, KMnO4
c(1/5 KMnO4) = 0.1 mol/L
Standard:
NaOH: Potassium hydrogen phthalate
KMnO4: sodium oxalate, Na2C2O4
Results:
Method
Measured
User
Instruments: METTLER TOLEDO DL58
Printer EPSON SC600
hcl1:
Titration of HCl
hydr1:
Redox titration of H2O2
Methods:
Accessories: Second burette drive DV90 Second burette DV1010
pH Option
Titration beakers ME-101974
Indication:
hcl1 Back titration of NH3
08/11/2000
14:03
J. Maag
DG111-SC
DM140-SC
08/11/2000
14:01
ALL RESULTS
No.
1
ID
Sample size and results
HCl/H2O2
0.777
R1 = 1.188
Method
Measured
User
g
%
hydr1 H2O2 determination
08/11/2000
14:07
J. Maag
HCl Content
08/11/2000
14:03
ALL RESULTS
No.
1
ID
Sample size and results
HCl/H2O2
0.777
R1 = 2.075
Page 38/100 METTLER TOLEDO DL5x and DL7x Titrators
g
%
H2O2 content
Electronics and electroplating applications
Method hcl1
Method
hcl1
Version
Method hydr1
Titration of HCl
08/11/2000 14:01
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
Method
. . . hcl1
. . . Titration of HCl
. . . 08/11/2000 14:01
.
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.
HCl/H2O2
Weight
0.02
2.0
36.35
1
Stand 1
Manual
. . . 50
. . . 10
.
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.
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.
.
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.
.
NaOH
1.0
DG111
pH
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
1.0
3.0
30.0
.
.
.
.
.
.
.
.
.
.
.
.
100.0
No
No
Positive
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
10.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=Q*C/m
C=M/(10*z)
3
%
HCl Content
Yes
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
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.
.
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.
.
.
.
.
.
.
.
.
.
.
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Remarks
1.
2.
3.
Method hcl1: det. of HCl by direct titration.
Add 1 mL 10% HNO3 for peroxide determination
Method hydr1: determination of H2O2 by redox
titration with 1/5 KMnO4.
Electronics and electroplating applications
hydr1
Version
H2O2 determination
08/11/2000 14:03
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set)[mV]
. . . . . . .
∆V(min)[mL]
. . . . . . .
∆V(max)[mL]
. . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . hydr1
. . . H2O2 determination
. . . 08/11/2000 14:03
.
.
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.
.
.
HCl/H2O2
Weight
0.02
2.0
34.02
1
Stand 1
Manual
. . . 50
. . . 10
.
.
.
.
.
.
.
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.
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.
.
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.
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.
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.
.
.
.
1/5 KMnO4
0.1
DM140
mV
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
1.0
3.0
15.0
.
.
.
.
.
.
.
.
.
.
.
.
2000.0
No
No
Positive
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
8.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=Q*C/m
C=M/(10*z)
3
%
H2O2 content
Yes
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
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.
.
.
.
.
.
Printer
No
Yes
Yes
Yes
No
Yes
Yes
No
No
No
No
No
Disposal
The sample to be classified as special waste.
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author:
Judy Maag
METTLER TOLEDO DL5x and DL7x Titrators Page 39/100
METTLER TOLEDO
M181
Back-titration of aluminum in acidic bath
Sample:
Acid mixture, 1 mL
Substance:
Aluminium, Al, 15 g/L
Sulfuric acid, H2SO4
Oxalic acid, H2C2O4
Instruments: METTLER TOLEDO DL58
Printer
Methods:
Accessories:
Preparation: 1.
20 mL deion. water
2.
20 mL buffer solution pH 4
Indication:
3.
Dispense exactly 20 mL
0.1 mol/L EDTA
4. Warm up during 10 min.
until boiling point.
Titrant:
Zinc sulfate, ZnSO4
c(ZnSO4) = 0.1 mol/L
Standard:
ZnSO4: EDTA Standard
EDTA: ZnSO4 Standard
Results:
Sample
Al content
Acidic bath
(g/L)
n = 4
40001
Glass beakers ME-101446
Additional DV1020 burette
- Hg-DM141
(Amalgamated DM141)
- 3 drops 0.05 mol/L HgEDTA
Comments
flat titration
curve
x
srel
15.434
0.66%
DL40 Appl. no. 315
Sample
Al Purity
Comments
KAl(SO4)2•12 H2O
(%)
n = 5
x
srel
99.542
0.05%
INC = 0.1 mL
Threshold= 100mV/mL
∆E = 0.5 mV
∆t = 3.0
DL40 Appl. no. 110
Page 40/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
40001
Version
Remarks
Aluminium
11/01/2001
Aluminium acidic bath (Elox bath)
16:30
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
• This acidic bath contains aluminium, sulfuric and
. . . 40001
. . . Aluminium
. . . 11/01/2001
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
16:30
Al/H2SO4/C2O42Fixed volume
1.0
26.982
1
Stand 1
Manual
. . . 50
. . . 10
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
ZnSO4
0.1
HgDM141
mV
Yes
5.0
INC
0.3
Equilibrium controlled
0.5
3.0
3.0
30.0
.
.
.
.
.
.
.
.
.
.
.
.
25.0
No
No
Positive
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
20.0
No
No
Yes
1
No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
Standard
No
No
Yes
neq=0
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
.
R=(H1-Q)*C/m
C=M/z
3
g/L
Al Content
Yes
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
. 0
.
.
. No
.
.
.
.
.
.
.
.
.
.
.
.
.
.
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.
.
.
.
.
.
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.
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.
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.
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.
.
.
.
.
.
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Disposal
The sample to be classified as special waste (Hg).
Other titrators
oxalic acid.
• The method was developed on the DL40 titrator
(see DL40 applications No. 3, 110, 315) and has
been adapted for the DL5x- and DL7x-titrators.
Sample preparation
1) Add 20 mL deionized water to the sample.
2) Add 20 mL buffer solution pH 4 to avoid formation
of aluminium hydroxide.
3) 20 mL 0.1 mol/L EDTA are dispensed using the
auxiliary function "Dosing" of the titrator.
4) The sample beaker is heated to boiling during 10
minutes since the complexation of aluminium with
EDTA is very slow at room temperature. Cover the
glass titration beaker during heating.
5) Add three drops 0.05 mol/L Hg-EDTA
Procedure
• The aluminum concentration is determined by a
back titration of excess EDTA with zinc sulfate.
• A blank titration is performed before analysis. The
result (mmol) is stored as auxiliary value H1 and
used for the back-titration.
• The EDTA excess is titrated with method 40001.
Chemicals
• Buffer solution pH 4: Dissolve 120 mL glacial
acetic acid (i.e. 100%) and 54 g sodium acetate
trihydrate in a 1 L flask. Add 10 mL 0.05 mol/L
HgEDTA, and dilute to 1 L with deionized water.
• 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
and 0.05 mol/L Hg-acetate are mixed together. This
solution is used as an indicator for the titration and is
dissolved into the buffer solution instead of adding
three drops for each sample.
Amalgamation of DM141 electrode (Hg-DM141)
• Clean the DM141 electrode with 2 mol/L HNO3,
possibly polished , well rinsed and dried. The
DM141 is dipped for 1 minute into mercury. The
excess mercury is wiped off. Several titrations can
be indicated before re-amalgamation.
• Note: the Hg-DM141 is inactivated by hydrogen
peroxide, H2O2, and by S2-, CN- , .... .
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author:
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 41/100
Kees Mooibroek
METTLER TOLEDO
M182
Titration of sulphuric acid and aluminum in an electroplating bath
Sample:
Acidic bath, 2 mL
Substance:
Free sulfuric acid, H2SO4
(M = 98 ; z = 2)
Aluminium, Al(III)
(M = 26.98 ; z = 3)
Instruments: METTLER TOLEDO DL53
Epson matrix printer LX800
with serial inteface 8148
Accessories: Titration beakers ME-101974
Preparation: 50 mL deionized water
Titrant:
Sodium hydroxide, NaOH:
c(NaOH) = 1 mol/L
Standard:
Potassium hydrogen phtalate
(see application M531)
25002
Method:
Indication:
DG111-SC
Results:
Content (g/L)
Content
Results
n
srel
Free acid
as H2SO4:
287.180 g/L
4
0.134%
Aluminum:
1.857 g/L
3
1.323%
Comments
Test solution:
Content (g/L)
Free acid
as H2SO4:
49.042 g/L
Theoretical
content (g/L)
49 g/L
Content
Aluminum:
2.347 g/L
Theoretical
content (g)
Test solution:
5
0.219%
5
1.233%
2 mL 1 mol/L H2SO4
+ 2 mL Al2(SO4)3 2.3 g/L Al
2.3 g/L Al
Page 42/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
25002
Version
Remarks
Free acid + Al
26/01/2001 15:46
Title
Method ID . . . . . . . .
Title
. . . . . . . .
Date/time . . . . . . . .
Sample
Sample ID . . . . . . . .
Entry type . . . . . . . .
Volume [mL] . . . . . .
Molar mass M . . . . . . .
Equivalent number z . . .
Titration stand . . . . .
Temperature sensor . . . .
Stir
Speed [%] . . . . . . . .
Time [s] . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . .
Concentration [mol/L] .
Sensor . . . . . . . .
Unit of meas. . . . . .
Predispensing . . . . . .
Titrant addition . . . . .
∆E(set) [mV] . . . . .
∆V(min) [mL] . . . . .
∆V(min) . . . . . . . .
Measure mode . . . . . . .
∆E [mV] . . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Recognition
Threshold . . . . . . .
Steepest jump only . .
Range . . . . . . . . .
Tendency . . . . . . .
Termination
at maximum volume [mL]
at potential . . . . .
at slope . . . . . . .
after number EQPs . . .
Evaluation
Procedure . . . . . . .
Potential 1 . . . . . .
Potential 2 . . . . . .
Stop for reevaluation .
Condition . . . . .
Calculation
Formula . . . . . . . . .
Constant . . . . . . . . .
Decimal places . . . . . .
Result unit . . . . . . .
Result name . . . . . . .
Statistics . . . . . . . .
Calculation
Formula . . . . . . . . .
Constant . . . . . . . . .
Decimal places . . . . . .
Result unit . . . . . . .
Result name . . . . . . .
Statistics . . . . . . . .
Calculation
Formula . . . . . . . . .
Constant . . . . . . . . .
Decimal places . . . . . .
Result unit . . . . . . .
Result name . . . . . . .
Statistics . . . . . . . .
Report
Output . . . . . . . . . .
Results . . . . . . . . .
All results . . . . . . .
Raw results . . . . . . .
Table of measured values .
Sample data . . . . . . .
E - V curve . . . . . . .
∆E/∆V - V curve . . . . .
∆2E/∆V2 - V curve . . . . .
log ∆E/∆V - V curve . . .
E - t curve . . . . . . .
V - t curve . . . . . . .
∆V/∆t - t curve . . . . .
• The method was developed on the DL25 titrator
. . . . . 25002
. . . . . Free acid + Al
. . . . . 26/01/2001 15:46
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H2SO4/Al
Fixed volume
2.0
26.98
3
Stand 1
Manual
. . . . . 50
. . . . . 10
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NaOH
1.0
DG111
As installed
No
Dynamic
4.0
0.02
0.2
Equilibrium controlled
0.5
1.0
3.0
30.0
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4
No
No
Positive
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4.0
No
No
No
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Standard
No
No
Yes
neq=0
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R1=Q1*C1/m
C1=98.07/2
3
g/L
H2SO4
Yes
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R2=Q2*C2/m
C2=M/z
3
g/L
Aluminum
Yes
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. 0
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. No
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and has been adapted for the DL5x-/7x-titrators.
Procedure
• The determination of free acid and aluminum in an
acidic aluminun bath is determined with a single
titration using sodium hydroxide.
• The titration curve gives three equivalence
points:
1st EQP:
Neutralization of free acid
= Na2SO4 + 2 H2O
H2SO4 + 2 NaOH
2nd EQP: Precipitation of aluminum hydroxide
Al2(SO4)3 + 6 NaOH = 2 Al(OH)3 + 3 Na2SO4
3rd EQP: Dissolution of Al(OH)3
Al(OH)3 + NaOH =
Al(OH)4- + Na+
Literature
• Application no. M531, in Application brochure 18,
Titration curves: standard solution
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Disposal
Neutralization with HCl, special waste
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Electronics and electroplating applications
Author: Roland Böhlen, MT-Switzerland
METTLER TOLEDO DL5x and DL7x Titrators Page 43/100
METTLER TOLEDO
M183
Determination of nickel and cadmium by complexometry
Sample:
Standard solutions, 5 mL
Substance:
Cadmium, Cd
Nickel, Ni
Instruments: METTLER TOLEDO DL58
Printer
40002
Methods:
Preparation: A)
Only Cd, masking of Ni:
- 10 mL buffer pH 10 solution
- 0.5 g dimethyl glyoxime,
sodium salt octahydrate
(C4H6N2Na2O2 • 8 H2O)
- 40 mL deionized water
Accessories: Titration beakers ME-101974
DV1010 burette
Indication:
- 3 drops 0.05 mol/L HgEDTA
for each sample.
B)
Ni, Cd, Ni + Cd:
- 10 mL buffer pH 10 solution
- 40 mL deionized water
Titrant:
EDTA, e.g. c(EDTA) = 0.1 mol/L
Standard:
ZnSO4
- Hg-DM141
(Amalgamated DM141)
Results:
Sample
Titrant
mol/L
Increment
mL
Result
g/L
n
srel
%
Comments
Ni
0.1
0.1
5.8273
5
0.23
Steep titration curve
Cd
0.1
0.05
11.433
5
0.70
Steep titration curve
Ni + Cd
1 : 1
0.1
0.1
0.1
5.731(Cd)
2.921 (Ni)
5
5
0.22
--
Steep titration curve
Ni + Cd
1 : 1
0.1
0.1
0.1
0.1
11.618 (Cd)
5.8060 (Ni)
2
4
---
Steep titration curve
Ni + Cd
1 : 100
0.1
0.1
0.05
11.33 (Cd)
0.061 (Ni)
5
5
0.12
--
Ni + Cd
100: 1
0.01
0.1
0.05
0.1124 (Cd)
5.768 (Ni)
5
5
1.82
--
Cd Stand.
solution
0.01
0.05
Titerfactor
0.8944
4
0.69
Page 44/100 METTLER TOLEDO DL5x and DL7x Titrators
Less accurate result
Curve less steep (Cd)
Electronics and electroplating applications
Method
Method
40002
Version
Remarks
Ni + Cd
12/01/2001
• The method was developed on the DL40 titrator (see
15:50
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Auxiliary value
ID . . . . . . . . . . . . . .
Constant . . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . 40002
. . . Ni + Cd
. . . 12/01/2001
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15:50
Ni/Cd
Fixed volume
5.0
112.41
1
Stand 1
Manual
. . . 50
. . . 10
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EDTA
0.1
HgDM141
mV
Yes
1.0
INC
0.1
Equilibrium controlled
0.2
2.0
3.0
30.0
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150
No
No
Negative
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=Q*C/m
C=M/z
3
g/L
Cd Content
Yes
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R2=Q
3
mmol
Cd Content
Yes
DL40 applications No. 317) and has been adapted
for the DL5x- and DL7x-titrators.
Sample preparation
A) Cadmium determination:
1) Add 10 mL buffer solution pH 10.
2) Add 0.5 g dimethylglyoxime disodium salt to
mask nickel ions.
3) Add 40 mL deionized water.
4) Add 3 drops 0.05 mol/L HgEDTA.
B) Ni determination:
1) Add 10 mL buffer solution pH 10.
2) Add 40 mL deionized water.
3) Add 3 drops 0.05 mol/L HgEDTA.
Procedure
• Cd content:
1) Ni is masked with dimethylglyoxime disodium salt. The sample is titrated with method
40002.
2) The Cd content is stored as auxil. value H6.
• Ni content:
1) EDTA forms complexes with both Ni and Cd.
2) To distinguish both metal ions, the Cd content is
accounted for as a blank value in the calculation:
R = (Q - H6)*C/m .
3) Since nickel is determined, C = M(Ni)/z, and
therefore M = 58.59 .
. . . mmol Cd
. . . H6=R2
Chemicals
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• Buffer solution pH 10: 70 mL of concentrated ammonia solution (d=0.9 g/mL) and 70 g ammonium
chloride (or 110 g NH4NO3) are dissolved in a 1 L
flask with deionized water.
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
• 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
and 0.05 mol/L Hg-acetate are mixed together.
Amalgamation of DM141 electrode (HgDM141)
The sample to be classified as special waste (Hg).
• Clean the DM141 electrode with 2 mol/L HNO3,
possibly polished , well rinsed and dried. The
DM141 is dipped for 1 minute into mercury. The
excess mercury is wiped off. Several titrations can
be indicated before re-amalgamation.
Other titrators
• Note: the Hg-DM141 is inactivated by hydrogen
peroxide, H2O2, and by S2-, CN- , .... .
Disposal
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Electronics and electroplating applications
Author:
Kees Mooibroek
METTLER TOLEDO DL5x and DL7x Titrators Page 45/100
METTLER TOLEDO
M184
Determination of cadmium in alkaline baths
Sample:
1 mL alkaline bath
Substance:
Cadmium, Cd
Instruments: METTLER TOLEDO DL67
Printer EPSON LX400
METTLER TOLEDO ST20A
Method:
Preparation: - 50 mL deion. water.
- 0.25 g 1:500 Murexide:NaCl
trituration
Titrant:
EDTA
c(EDTA) = 0.1 mol/L
Standard:
0.1 mol/L ZnSO4
BL65
Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
Indication:
DP660 Phototrode at sensor 2
with
DIN-Lemo adapter ME-89600
Results:
Method
User
Measured
BL65 Cadmium im alk. Elektrolyt
28-02-1994
21-02-1994
9:48
9:57
RESULTS
No
ID1
ID2
1/1
Sample amount and results
1/2
1.0
R1 = 24.06
1.0
R1 = 23.08
1.0
R1 = 24.04
1/3
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
n
x
s
srel
Page 46/100 METTLER TOLEDO DL5x and DL7x Titrators
=
=
=
=
mL Fixed volume U
g/L
Cadmium
mL Fixed volume U
g/L
Cadmium
mL Fixed volume U
g/L
Cadmium
3
23.73
g/L
0.560119 g/L
2.361
%
Cadmium
Cadmium
Electronics and electroplating applications
Remarks
Method
Method
BL65
Version
Cadmium im alk. Elektrolyt
21-02-1994
9:48
Title
Method ID . . . . . . . . . . . . . BL65
Title . . . . . . . . . . . . . . . Cadmium im alk.
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1
. . . .
Volume [mL]
. . . .
Titrant addition . . . .
dE(set) [mV] . . . . .
Limits dV . . . . . .
dV(min) [mL] . . .
dV(max) [mL] . . .
Measure mode . . . . . .
dE [mV] . . . . . . .
dt [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Record
Output unit . . . . . . . .
All results . . . . . . . .
Elektrolyt
. . . . 21-02-1994
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9:48
3
ST20 1
Fixed volume U
1.0
112.40
1
Manual
. . . . 50
. . . . 10
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EDTA
0.1
DP660
mV
EQP
mL
0.5
DYN
8.0
Absolute
0.05
0.2
EQU
0.5
1.0
3.0
30.0
50.0
20.0
Yes
1
Asymmetric
. . . . H 2O
. . . . 10.0
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Cadmium
R=Q*C/m
C1=M/z
g/L
2
. . . . R1
. . . . Yes
. . . . Yes
. . . . Printer
. . . . Yes
Sample preparation
1) The sample is diluted and then titrated with 0.1
M EDTA. No pH buffer is added, the bath is alkaline.
2) Use a trituration 1:500 murexide: NaCl.
3) Add the indicator before starting analysis. Keep
sample free of air bubbles during titration. Air
bubbles and undissolved impurities affect with the
photometric indication.
4) Adjust the DP660 at 1000 mV in deionised water
before starting titration (100% transmission).
Titration
• Cd(II) ions forms complexes with the indicator
murexide in alkaline:
Cd 2+ + Murexide - = Cu-Murexid +
• By titration with EDTA, Murexide is diplaced
by EDTA and forms a complex with Cd ions in
an alkaline, neutral or weakly acid medium:
Cd 2+ + H2-EDTA2- = Cd-EDTA2- + 2 H+
Disposal
Classify as special waste (heavy metals)
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
water. To aliquots of 5 mL add 10 mL buffer ph 4.5
solution and 5 drops HgEDTA
E-V curve
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
Lit.: DL40 appl. note 1986, Appl. Database 40.8603
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Electronics and electroplating applications
Authors: Application Laboratory MT-Germany
METTLER TOLEDO DL5x and DL7x Titrators Page 47/100
METTLER TOLEDO
M185
Iodometric titration of Cr(VI) in an electroplating bath
Instruments: METTLER TOLEDO DL70
Chromium (VI) bath, 0.1 mL
METTLER TOLEDO ST20A
(diluted/aliquot, see sample prepaMETTLER TOLEDO AT261
ration)
Printer EPSON FX850
with serial interface
Substance: Cr(VI) as CrO3
M = 99.99 ; z = 3
Method:
vd03
Preparation: - 50 mL deionized water
Accessories: Titration beakers ME-101974
- Sulfuric acid 1:1, 10 mL
Peristaltic pump SP40
- Potassium iodide, KI, 1.5 g
Sample:
Titrant:
Sodium thiosulphate, Na2S2O3
c(Na2S2O3)=0.1 mol/L
Standard:
Potassium iodate, KIO3
Results:
METTLER DL70
Indication:
DM140 at sensor 2
Titrator
vd03 Chromium (VI)
23-Nov-1989 12:04
SW Version 1.2
measured
Titrator
User
23-Nov-1989 12:32
Mettler Tiel
J.vd Ouweland
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
No
1/1
1/2
1/3
1/4
1/5
1/6
1/7
1/8
Identification
Volume
0.1
0.1
0.1
0.1
0.1
0.1
0.1
0.1
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Results
mL
mL
mL
mL
mL
mL
mL
mL
n
x
s
srel
Page 48/100 METTLER TOLEDO DL5x and DL7x Titrators
149.94
150.01
150.08
151.52
150.41
150.27
150.06
149.64
= 8
= 150.24
= 0.565
= 0.376
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
CrO3
CrO3
CrO3
CrO3
CrO3
CrO3
CrO3
CrO3
g/L
g/L
%
CrO3
CrO3
Electronics and electroplating applications
Remarks
Method
Method
vd03
Version
Chromium (VI) in Cr-bath
23-Nov-1989
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing
. . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V [mL] . . . .
∆V(min) [mL] . . .
∆V(max) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Record
Short-form method . . . . .
Results last sample . . . .
All results . . . . . . . .
Table of measured values . .
E - V curve . . . . . . . .
12:04
. . . . vd03
. . . . Chromium (VI) in Cr-bath
. . . . 23-Nov-1989
12:04
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8
ST20
Fixed volume U
0.1
99.99
3
. . . . 60
. . . . 10
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Na2S2O3
0.1
DM140-SC
mV
EP
mL
2.0
DYN
8.0
Absolute
0.02
0.2
EQU
0.5
1.0
3.0
30.0
300.0
20.0
Yes
1
Standard
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CrO3
R=Q*C/U
C=M/z
g/L
2
. . . . H 2O
. . . . 10.0
. . . . R1
. . . . Yes
. . . . Yes
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Sample preparation
1) 1 mL chromium bath is diluted with deionized water to 10 mL. 1 mL aliquot corresponds to 0.1 mL
original sample.
2) 1 mL aliquot is diluted with 20 mL deion. water.
3) 10 mL sulfuric acid 1:1 are added.
4) Add 1.5 g potassium iodide (KI) and cover the beakers to avoid loss of iodine.
5) The sample solution is kept in the dark during 5-10
minutes.
6) During this time, Cr(VI) is reduced by excess iodide (I-) to Cr(III):
2 Cr6+ + 6 I - → 2 Cr3+ + 3 I2 (z = 3)
The amount of iodine I2 formed is proportional to
the Cr(VI) content.
Titration of iodine
The formed I2 is then titrated with Na2S2O3:
2 S2O32- + I2 →
• Stir moderately to avoid loss of I2
Table of measured values:
Volume
mL
E1
E2
Yes
Yes
Yes
Yes
Yes
Application note:
Cr(VI) in etching solutions
A DP550 Phototrode with starch solution as an indicator can be used instead of a DM140 electrode if the
solution is clear enough.
Sample preparation:
See above. In addition, 1 g NH4HF2 is added as a masking agent for Al.
(Literature: DL40 Application no. 306)
S4O62- + 2 I-
EQP1
Increment
mL
0.000
1.143
1.714
2.000
2.200
2.400
2.600
2.800
3.000
3.200
3.400
3.600
3.800
4.000
4.200
4.367
4.446
4.474
4.494
4.514
4.535
1.143
0.571
0.286
0.200
0.200
0.200
0.200
0.200
0.200
0.200
0.200
0.200
0.200
0.200
0.167
0.079
0.028
0.020
0.020
0.021
Signal
mV
298.6
296.6
295.1
294.1
293.3
292.4
291.4
290.2
288.7
287.3
285.2
282.8
279.7
275.6
268.8
257.4
243.5
227.5
190.7
168.6
160.8
Change
mV
-2.0
-1.5
-1.0
-0.8
-0.8
-1.0
-1.2
-1.4
-1.5
-2.1
-2.4
-3.1
-4.1
-6.8
-11.4
-13.9
-15.9
-36.8
-22.2
-7.8
1st deriv.
mV/mL
-1.8
-2.5
-3.6
-4.2
-4.1
-5.2
-6.2
-7.1
-7.3
-10.5
-12.0
-15.5
-20.3
-34.2
-68.0
-176.5
-569.5
-1840.2
-1108.1
-371.3
Time
min:s
0:03
0:09
0:14
0:19
0:23
0:28
0:35
0:40
0:45
0:50
0:54
0:59
1:03
1:08
1:12
1.18
1.22
1:29
1:43
1:53
2:01
E-V curve:
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
M186
Determination of Cr(III) by back-titration in an electroplating bath
Sample:
Chromium (III) bath, 5 mL
Substance:
Cr(III) as Cr2O3
M = 151.99 ; z = 3
Preparation: - 10 mL nitric acid 1:1
- 50 mL 0.05 mol/L acid
cerium sulphate solution
- 5 min. heating, 50°C
Titrant:
Sodium nitrite, NaNO2
c(1/2 NaNO2) = 0.2 mol/L
Standard:
For cerium sulphate (see M543):
Di-sodium oxalate, C2Na2O4
For sodium nitrite (see M544):
Sulphanilic acid, C6H7NO3S
Instruments: METTLER TOLEDO DL55
METTLER TOLEDO ST20A
Printer EPSON LX400
Method:
40003
Accessories: Titration beakers ME-101446
Peristaltic pump SP250
1 burette DV1020
Indication:
DM140
Results:
Sample
Cr2O3 content
Cr bath
(g/L)
Comments
n = 2
x
srel
4.2782
--
Page 50/100 METTLER TOLEDO DL5x and DL7x Titrators
VEQ: 10.527 mL
DL40 Appl. no. 308
Electronics and electroplating applications
Method
Method
40003
Version
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Pump . . . . . . . . . . .
Rinse . . . . . . . . . . .
Solvent . . . . . . . .
Volume
. . . . . . . .
Conditioning . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
Disposal
Remarks
Cr(III) as Cr2O3
16/01/2001 10:10
. . . 40003
. . . Cr(III) as Cr2O3
. . . 16/01/2001 10:10
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Cr2O3
Fixed volume
5.0
152
3
ST20A
No
Yes
H 2O
10.0
No
Manual
. . . 50
. . . 10
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1/2 NaNO2
0.2
DM140
mV
to volume
2.0
0
Incremental
0.1
Equilibrium controlled
0.5
1.0
3.0
30.0
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300
No
No
Negative
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=(H2-Q)*C/m
C=M/(2*z)
4
g/L
Cr2O3
Yes
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R2=Q
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R3=VEQ
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
2
mmol
Cr2O3
Yes
3
mL
Titrant cons.
Yes
Special waste
Other titrators
• The method was developed on the DL40 titrator (see
DL40 applications No. 308) and has been adapted
for the DL5x- and DL7x-titrators.
• The Cr(III) content is expressed as Cr2O3 and is
detemined by back titration after addition of excess
cerium sulphate solution.
Sample preparation
1) Add 10 mL nitric acid 1:1 to 5 mL chromium bath
in a glass beaker.
2) 50 mL acid cerium sulphate solution c(Ce(SO4)2
= 0.05 mol/L) are added by using the dispensing
function of the titrator. This corresponds to 2.5
mmol/L equivalent Ce(IV)
3) The sample solution is heated during 5 minutes at
50°C. During this time, Cr(III) is oxidized by excess Ce (IV) to Cr(VI):
3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+ (z = 3)
whereas Ce(IV) is reduced to Ce(III):
Ce4+ → Ce3+ + e-
Procedure
1) A Ce(IV)-blank is determined using a similar method as for the determination of Cr(III). The blank
value is stored as auxiliary value H2 (mmol).
2) Cr(III) is then determined by a back-titration of
excess Ce(IV) using sodium nitrite as a titrant:
2Ce4+ + NO2- + Η2Ο → 2Ce3+ + NO3- + 2Η+
(z =2)
Chemicals
• 0.05 mol/L acidic cerium sulphate solution: Either
20.22 g Ce(SO4)2•4H2O or 31.63 g Ce(NH4)4(SO4)4•
2H2O are dissolved in 500 mL 1 mol/L sulphuric
acid in a 1 L flask. Heat it p to 70°C in a water bath.
After cooling to room temperature, fill to the mark
with deionized water.
Literature
• DL40 application no. 308, 1985
• Applications M543 and M544, in Application
brochure No. 18., "Standardization of Titrants",
DL50 Graphix, DL53/DL58, DL70ES, DL77.
Author: P. Rast, MT Switzerland
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 51/100
METTLER TOLEDO
M187
Chromium and vanadium in a K2Cr2O7 / V2O5 mixture
Sample:
Aqueous acid solution of K2Cr2O7
and V2O5 , 25 mL
Substance:
Cr(VI) as K2Cr2O7
(M = 294.19 ; z = 6)
V(V) as V2O5
(M = 181.88 ; z = 2)
Instruments: METTLER TOLEDO DL53
Epson matrix printer LX800
with serial inteface 8148
25001
Method:
Accessories: Titration beakers ME-101446
Indication:
Preparation: See next page (Remarks)
Titrant:
Fe(NH4)2(SO4)2 • 6H2O
M = 392.14
c(FAS) = 0.1 mol/L
Standard:
Potassium dichromate, K2Cr2O7
(see application M548)
DM140
(FAS):
Results:
K2Cr2O7 + V2O5
n
srel
K2Cr2O7
V 2O 5
n
srel
0.86956
5
0.318
0.6195
0.25008
4
0.2079
0.3037
0.2274
Theoretical
content (g)
0.3067
0.232
Recovery rate (%)
99.020
98.01
Content (mmol)
aliquot
Total content (g)
(10 x aliquot)
Reactions
1)
1st FAS titration:
1.1
6 Fe2+ + Cr2O72- + 14 H+ → 6 Fe3+ + 2 Cr3+ + 7 H2O
where
Cr2O72- + 14 H+ + 6 e- = 2 Cr3+ + 7 H2O
1.2 2
Fe2+ + V5+ = V4+ + Fe3+
2)
V4+ to V5+:
5 V4+ + MnO4- + 8 Η+ = 5 V5+ + Mn2+ + 4 Η2O
3)
2nd FAS titration: see 1.2
Page 52/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
25001
Version
Cr/V
16/01/2001
Remarks
• The method was developed on the DL25 titrator
15:30
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
∆V(min) . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . 25001
. . . Cr/V
. . . 16/01/2001
.
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15:30
K2Cr2O7/V2O5
Fixed volume
25.0
294.26
6
Stand 1
Manual
. . . 50
. . . 10
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FAS
0.1
DM140
mV
to volume
2.0
15
Dynamic
4.0
0.1
0.2
Equilibrium controlled
0.5
1.0
5.0
30.0
.
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200
No
No
Negative
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=Q
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R2=VEQ
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. 0
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. No
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5
mmol
K2Cr2O7/V2O5
Yes
3
mL
Titrant cons.
Yes
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
(see DL25 appl. no. 21) and has been adapted for
the DL5x- and DL7x-titrators.
• The sample is dissolved in sulphuric acid. It is
oxidized with KMnO4 to ensure that chromium
and vanadium are present in their highest oxidation
state. The first titration with FAS gives the sum of
Cr and V in mmol. Iron (Fe(II)) reduces Cr(VI) to
Cr(III), while vanadium(V) is reduced to V(IV).
In a second step , V(IV) is again oxidized by KMnO4
to V5+ and titrated with FAS. The difference between
the first and the second FAS titration accounts for
the chromium content.
Sample preparation
1) 0.5 g of sample are heated in 30 mL 10% sulphuric acid until complete dissolution.
2) In a 250 mL flask dilute with deionized water.
3) Take 25 mL aliquots and add KMnO4 solution
dropwise (KMnO4: 5g/100mL).
4) Add 5 mL conc. HCl to eliminate excess
KMnO4 present in the solution.
5) Heat until violet permanganate colour disappears, and cool to room temperature.
6) 1st titration with FAS (V2O5 + K2Cr2O7).
7) Add again KMnO4 until violet is persistent.
8) Excess KMnO4 is eliminated by adding KNO2
solution dropwise (KNO2 = 1g/100 mL).
9) Add 0.5 g urea to eliminate excess KNO2.
10) 2nd titration with FAS (V2O5).
11) The difference between first and second result
gives the chromium content.
Chemicals
•
Special waste
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77.
Electronics and electroplating applications
(M=392.14):
Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000
mL flask with 10% sulphuric acid and fill to the
mark with deionized water.
Literature
•
•
•
Disposal
0.1 M Fe(NH4)2(SO4)2 • 6H2O
•
DL25 application no. 21, in DL25 Application
Brochure "Chemicals", ME-51724629 (1994).
Application no. M548 and M544, in Application brochure 18, "Standardization of Titrants",
2000.
"Metallurgische Analysen", József Mika, Budapest
"Handbuch für das Eisenhüttenlaboratorium", 2.
Band, Chemikerausschuss des Vereins Deutscher
Eisenhüttenleute.
Author: Maria José Schmid
METTLER TOLEDO DL5x and DL7x Titrators Page 53/100
METTLER TOLEDO
M188
Determination of Cr(VI) in an electroplating bath by Fe(II) titration
Sample:
Cr-electroplating bath, 0.2 mL
Substance:
Cr(VI)
M = 99.99 ; z = 3
Instruments: METTLER TOLEDO DL50
Printer HP DeskJet 500
02
Method:
Accessories: Titration beakers ME-101974
Preparation: 50 mL deionized water
Titrant:
Fe(NH4)2(SO4)2 • 6H2O (FAS):
M = 392.14, c(FAS) = 0.1 mol/L
Standard:
Potassium dichromate, K2Cr2O7
(see application M548)
DM140
Indication:
Results:
METTLER TOLEDO DL50
Method
Measured
User
Titrator
V2.3
Laboratorium Helio Repro BV
Kerkrade
02
Chroom(VI)-bep in Cr-baden 03-11-2000
01-12-2000 13:15
W.Jongen
10:58
ALL RESULTS
No.
ID
Sample size and results
1
CrHe128/11
2
CrHe128/11
3
CrHe128/11
0.2
R1 = 320.31
0.2
R1 = 320.55
0.2
R1 = 320.10
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Page 54/100 METTLER TOLEDO DL5x and DL7x Titrators
n
x
s
srel
mL
g/L
mL
g/L
mL
g/L
=
=
=
=
Chroomzuur
Chroomzuur
Chroomzuur
3
320.32 g/L
0.22772 g/L
0.071
%
Chroomzuur
Chroomzuur
Electronics and electroplating applications
Method
Method
02
Version
Title
Method ID
Title
Chroom(VI)-bep in Cr-baden
03-11-2000 10:58
. . . . . . . . . . . . . 02
. . . . . . . . . . . . . Chroom(VI)-bep in
Cr-baden
. . . . . . . . . . . . . 03-11-2000 10:58
Date/time
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
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CrHe128/11
Fixed volume
0.2
99.99
3
Stand 1
Manual
. . . 30
. . . 15
Remarks
• Cr(VI) is reduced to Cr(III) by the addition of titrant: Fe(II) is oxidized to Fe(III) according to:
3 Fe2+ + Cr6+ = 3 Fe3+ + Cr3+
Chemicals
•
Fe(NH4)2(SO4)2 • 6H2O
(FAS), 0.1 mol/L:
Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000
mL flask with 10% sulphuric acid and fill to the
mark with deionized water.
.
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.
(NH4)2Fe(SO4)2
0.1
DM140
mV
to volume
17
60
Dynamic
4.0
0.05
0.08
Equilibrium controlled
1.0
1.0
3.0
20.0
Literature
.
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300
No
No
Negative
Table of measured values:
.
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25.0
No
No
Yes
1
No
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.
Standard
No
No
Yes
.
.
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.
R=Q*C/m
C=M/z
2
g/L
Chroomzuur
Yes
.
.
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.
. 0
.
.
. No
.
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. 0
.
.
. No
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Printer+Computer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
•
Application no. M548 in Application brochure18,
"Standardization of Titrants", 2000.
Volume
mL
Increment
mL
Signal
mV
Change
mV
0.0000
9.7140
14.5710
17.0000
17.0800
17.1600
17.2400
17.3200
17.4000
17.4800
17.5600
17.6400
17.7200
17.8000
17.8800
9.7140
4.8570
2.4290
0.0800
0.0800
0.0800
0.0800
0.0800
0.0800
0.0800
0.0800
0.0800
0.0800
0.0800
979.0
973.2
975.1
984.4
984.2
984.2
984.2
984.5
984.5
985.1
985.1
985.6
986.1
986.2
986.8
-5.8
1.9
9.2
-0.2
0.0
0.1
0.3
0.0
0.6
0.1
0.5
0.5
0.1
0.5
-0.6
0.4
3.8
-2.4
0.0
0.8
3.2
0.0
7.3
0.8
0.5
6.5
1.6
6.5
0:03
0:26
1:09
2:16
2:19
2:23
0:26
2:30
2:33
2:36
2.40
2:44
2:49
2:53
2:57
19.7200
19.8000
19.8500
19.9300
EQP1 19.9800
20.0300
20.0800
0.0800
0.0800
0.0500
0.0800
0.0500
0.0500
0.0500
987.6
967.2
960.1
866.5
596.5
575.8
564.9
-2.5
-20.4
-7.1
-93.6
-270.0
-20.7
-10.9
-31.5
-254.4
-142.2
-1170.4
-5399.8
-413.6
-218.4
5:33
5:54
6:14
6:35
6:41
7:12
7:15
ET1
ET2
1st deriv.
mV/mL
Time
min:s
E-V curve:
Disposal
Special waste
Other titrators
DL53, DL58, DL70ES, DL77.
Electronics and electroplating applications
Author: F. Saes, MT-NL/ W. Jongen
METTLER TOLEDO DL5x and DL7x Titrators Page 55/100
METTLER TOLEDO
M189
Determination of free cyanide in a copper bath
Sample:
Copper bath,
aliquots of 1 mL from diluted
solution of 10 mL in 100 mL.
Substance:
Free cyanide, CNM = 26.02, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Accessories: Titration beakers ME-101974
Preparation: 5 mL potassium iodide, KI, 10%
40 mL deion. water
Titrant:
Silver nitrate, AgNO3
c(1/2 AgNO3) = 0.2 mol/L
Standard:
Sodium chloride
(see application M525)
25003
Indication:
DP550 Phototrode with
DIN-Lemo Adapter ME-89600
Results:
CN-
n
Comments
Mean value
26.84 g/kg
6
DL25 application note
in
Standard
deviation s
0.346 g/kg
Rel. standard
deviation srel
1.29 %
Page 56/100 METTLER TOLEDO DL5x and DL7x Titrators
DL25 Application brochure
"Petroleum products and
electroplating"
ME-51 724 627
Electronics and electroplating applications
Method
Method
25003
Version
Remarks
Free CN- in Cu bath
17-01-2001 10:50
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . 25003
. . . Free CN- in Cu bath
. . . 17-01-2001 10:50
.
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.
Cu bath
Fixed volume
1.0
26.01
1
Stand 1
Manual
. . . 50
. . . 10
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.
.
.
.
1/2 AgNO3
0.2
DP550
mV
to volume
1.5
20
Dynamic
4.0
0.02
0.2
Equilibrium controlled
0.5
1.0
5.0
30.0
.
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.
200
No
No
Negative
.
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.
.
.
.
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.
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.
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.
20.0
No
No
Yes
1
No
.
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.
Standard
No
No
Yes
neq=0
.
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.
R=Q*C/m
C=M/z
2
g/L
Sample content
Yes
.
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.
R2=R1*10
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.
R3=Q*C3
C3=M*1000/z
2
mg
CN in sample
No
.
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
2
g/L
Bath content
Yes
• The cyanid content determination in e.g. brass
electroplating bath is very important to achieve
optimum plating efficiency.
• The method was developed on the DL25 titrator and
has been adapted for the DL5x-/DL7x-titrators.
Sample preparation
1) 10 mL copper bath are diluted to 100 mL with
deionized water.
2) 1 mL aliquot is poured in the titration beaker.
3) Add 5 mL 10% potassium iodide solution (KI).
4) 40 mL deionized water is added to the sample.
Reaction
• A soluble complex Ag(CN)2 - is first formed by
the reaction between silver and cyanide ion:
•
•
Chemicals
•
•
•
•
Other titrators
•
Cyanide waste
Electronics and electroplating applications
10% Potassium iodide, KI: 50 g KI and 50 g
NaOH are dissolved in deionized water, and diluted to 500 mL in a volumetric flask.
Literature
Disposal
DL50 Graphix, DL53/DL58, DL70ES, DL77.
Ag+ + 2 CN- = Ag(CN)2 As long as free cyanide is still present, the solution remains clear, but the first excess of silver
causes formation of a white solid that mark the
endpoint:
Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
To obtain a accurate determination of the endpoint, potassium iodide is used as an indicator.
During titration, any silver iodide which would
tend to form will be kept in solution by the excess
of cyanide ion always present until the equivalence point is reached:
AgI + 2 CN- = [Ag(CN)2] - + IAfter the equivalence point, the formation of yellow silver iodide will lead to a turbidity increase
which indicates the end point.
Application note, DL25 Application Brochure
"Petroleum and electroplating", ME-51724627.
Vogel's textbook of quantitative inorganic
analysis, 4th edition, Longman Group Limited ,
1978.
D.A. Skoog, D.M. West, "Fundamentals of Analytical Chemistry", Holt, Rinehart, and Winston,
1969.
Application no. M525 in Application brochure18,
Author: R. Böhlen, MT Switzerland
METTLER TOLEDO DL5x and DL7x Titrators Page 57/100
METTLER TOLEDO
M190
Determination of free cyanide in a cyanidic zinc bath
Sample:
Cyanidic zinc bath,
aliquots of 1 mL
Substance:
Free cyanide, CNM = 26.02, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Preparation: 40 mL deionized water
5 mL 20% NaOH (5 mol/L)
Titrant:
Silver nitrate, AgNO3
c(1/2 AgNO3) = 0.2 mol/L
Standard:
Sodium chloride
(see application M525)
40004
Accessories: Titration beakers ME-101974
Indication:
DM141
Results:
Mean value
CN-
n
Comments
50.994 g/L
5
DL40 application no. 168
as NaCN, M=49
Rel. standard
deviation srel
0.37 %
Page 58/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
40004
Version
Remarks
Free CN- in Zn bath
18-01-2001 10:13
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
• The method was developed on the DL40 titrator
and has been adapted for the DL5x- and DL7xtitrators.
. . . 40004
. . . Free CN- in Zn bath
. . . 18-01-2001 10:13
.
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Zn bath
Fixed volume
1.0
26.01
1
Stand 1
Manual
. . . 50
. . . 10
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1/2 AgNO3
0.2
DM141
mV
to volume
1.0
10
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
1.0
5.0
30.0
.
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300
No
No
Positive
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15.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
.
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.
R=Q*C/m
C=M/z
2
g/L
Bath content
Yes
.
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.
R2=Q*C2
C2=M*1000/z
2
mg
CN in sample
Yes
.
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.
. 0
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. No
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Sample preparation
1) 1 mL zinc bath are diluted in a titration beaker
by adding 40 mL deionized water.
2) 5 mL 20% NaOH solution are added.
Reaction
• The following equation describes the interdependence of the different ions in a zinc bath:
Na2Zn(CN)4 + 4NaOH = Na2ZnO2 + 4NaCN + 2H2O
If excess sodium hydroxide is added, then all
cyanide is set free, and can be precipitated by
silver ions Ag+ added during titration:
Ag+ + 2 CN- = [Ag(CN)2] Note that silver forms in a first step the soluble
complex Ag(CN)2- . As long as free cyanide is
still present, the solution remains clear, but the
first excess of silver causes formation of a white
solid that mark the endpoint:
Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
•
The indication with the DM141 combined silver
electrode is superior to the traditional turbidimetric indication with potassium iodide.
•
The Zn content analysis is described in M191.
LIterature
• DL40 application no. 168
•
•
Vogel's textbook of quantitative inorganic analysis, 4th ed., Longman Group Limited , 1978.
Application no. M525 in Application brochure18,
"Standardization of Titrants", 2000.
E-V curve (DL40 application):
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
M191
Back-titration of zinc in a cyanidic zinc bath
Sample:
Cyanidic zinc bath,
aliquots of 1 mL
Substance:
Zn2+
M = 65.37, z = 1
Instruments: METTLER TOLEDO DL55
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Preparation: 50 mL deionized water
5 mL buffer solution pH 10
5 mL 37-40% formaldehyde sol.
Titrant 1:
Accessories: Titration beakers ME-101974
1 additional burette drive DV90
1 additional burette DV1005
(for ZnSO4)
EDTA,
c(EDTA) = 0.1 mol/L
Titrant 2:
Zinc sulphate, ZnSO4
c(ZnSO4) = 0.1 mol/L
Standard:
For EDTA: Zinc sulphate, ZnSO4
(see appl. M528)
For ZnSO4: EDTA
(see appl. M539)
40005
Indication:
DP550 Phototrode with
DIN-Lemo adapter ME-89600
0.5 mL Erio T, 0.1% solution.
Results:
Zn2+
n
Comments
Mean value
18.428 g/L
6
DL40 application no. 175
Rel. standard
deviation srel
0.08 %
Page 60/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
40005
Version
Remarks
Zn in Zn bath
18-01-2001 10:30
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Dispense
Titrant . . . . . . . . . . .
Concentration [mol/L] . . . .
Volume [mL] . . . . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
• The method was developed on the DL40 titrator
and has been adapted for the DL5x- and DL7xtitrators.
. . . 40005
. . . Zn in Zn bath
. . . 18-01-2001 10:30
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Zn bath
Fixed volume
1.0
65.37
1
Stand 1
Manual
. . . EDTA
. . . 0.1
. . . 6.0
. . . 50
. . . 20
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ZnSO4
0.1
DP550
mV
to volume
2.5
10
Incremental
0.02
Equilibrium controlled
0.2
2.0
5.0
30.0
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1000
No
No
Negative
.
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10.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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.
R=(QDISP-Q)*C/m
C=M/z
2
g/L
Bath content
Yes
.
.
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.
R2=R1*C2
C2=M*1000/z
2
mg
Zn in sample
Yes
.
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. 0
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. No
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
• Adjust the DP 550 at 1000 mV in deionised water
before starting titration (100% transmission).
Sample preparation
1) 1 mL zinc bath are diluted in a titration beaker
by adding 50 mL deionized water.
2) 5 mL buffer solution pH 10 are added
3) 5 mL 37-40% formaldehyde solution are added.
4) 0.5 mL indicator solution are added before titration.
Reaction
•
Zn is determined by back titration after addition
of an excess of EDTA (6 mL).
1. Zn(II) ions form complexes with EDTA:
Zn 2+ + H2-EDTA2- = Zn-EDTA2- + 2 H+
2. EDTA excess is titrated with 0.1 mol/L zinc sulphate solution according to the above reaction.
3. The colour change of Erio T in alkaline medium will be from blue to red when EDTA is titrated
with Zn(II).
Chemicals
•
Buffer solution pH 10:
70 g ammonium chloride, NH4Cl, and 570 mL
ammonium hydroxide, NH4OH, are dissolved
in 1000 mL volumetric flask. Diluto to the mark
with deionized water.
Literature
•
•
DL40 application no. 175
Applications no. M528 and 538 in Application brochure18, "Standardization of Titrants",
2000.
Disposal
Zinc is precipitated as zinc hydroxide with NaOH
or Ca(OH)2 and then filtrated (precipitate: special
waste).
Authors: U. Büchi / P. Schauwecker
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 61/100
METTLER TOLEDO
M175
Titration of gold -Au(III)- in a standard solution
Sample:
Standard solution, KAu(CN)2
5 mL aliquots
Substance:
Au3+
M = 196.97, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Preparation: 50 mL deionized water
Adjust to pH 3-5 with HNO3.
Titrant:
Silver nitrate, AgNO3
c(AgNO3) = 0.1 mol/L
Standard:
Sodium chloride
(see application M525)
40005
Accessories: Titration beakers ME-101974
Indication:
DM141
Results:
Au3+
n
Comments
Mean value
3.9978 g/L
5
DL40 application no. 8121
Theoretical
content
4.0134 g/L
Rel. standard
deviation srel
0.07 %
Page 62/100 METTLER TOLEDO DL5x and DL7x Titrators
1.46739 g KAu(CN)2 in 250 mL
in 250 mL deionized water
M(KAu(CN)2) = 288.07
Electronics and electroplating applications
Method
Method
40005
Version
Au(III)
18-01-2001
Remarks
• The method was developed on the DL40 titrator
16:30
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
and has been adapted for the DL5x- and DL7xtitrators.
. . . 40005
. . . Zn in Zn bath
. . . 18-01-2001 16:30
.
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.
Au-solution
Fixed volume
5.0
196.97
1
Stand 1
Manual
. . . 50
. . . 10
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.
AgNO3
0.1
DM141
mV
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
0.5
2.0
5.0
30.0
.
.
.
.
.
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.
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.
.
800
No
No
Positive
.
.
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.
.
.
10.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=Q*C/m
C=M/z
4
g/L
Au content
Yes
.
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.
R2=VEQ
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. 0
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. No
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Sample preparation
1) 5mL standard solution are diluted in a titration
beaker by adding 50 mL deionized water.
2) Adjust to pH 3-5 by carefully adding 1 mol/L
nitric acid (or more concentrated, if necessary).
CAUTION:
If the pH is lowered below pH 3, then HCN is
formed, which is extremely toxic! Therefore
work in a fume hood.
Reaction
•
Ag + + Au(CN)2- = AgAu(CN)2
Nitric acid is added to increase the steepness of
the potential jump at the equivalence point.
•
If the standard solution should contain chloride,
then the latter can be determined by continuing
the analysis until a second equivalence point is
found. This is due to the precipitation of silver
chloride in the sample solution.
•
Gold electroplating baths contain free cyanide.
Interference from free cyanide can be avoided
by adjusting the pH to 5-6 using 30-40% formaldehyde solution. After a waiting time of 15-20
minutes, the titration can be started.
3
mL
Consumption
Yes
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
Disposal
Special waste. CAUTION: cyanide is toxic!
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Gold is precipitated as AgAu(CN)2 during titration with silver nitrate:
Literature
•
DL40 application no. 8121, 1982.
•
Vogel's textbook of quantitative inorganic
analysis, 4th edition, Longman Group Limited ,
1978.
•
Application no. M525 in Application brochure18,
Authors: MT Analytical, Application laboratory
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 63/100
METTLER TOLEDO
M208
Determination of gold by precipitation reaction with hydroquinone
Sample:
Various gold alloys
0.02 - 0.08 g
Compound:
Gold, Au
M = 196.97; z = 3
Instruments: - METTLER TOLEDO DL70ES/77
- METTLER balance AT261
- Printer: HP Deskjet
Method:
Preparation: Solvent mixture
Accessories: - Two burette drives DV90
- Two 10 mL burettes DV910
- Glass beaker ME-101446
- Pump ME-65241
- Ultrasonic bath
conc. HCl: 5 mL / conc. HNO3: 1.5 mL
HCl 0.1 mol/L: 40 mL
Titrant 1:
Hydroquinone
c(1/2 C6H6O2) = 0.05 mol/L
Titrant 2:
Cerium(IV) sulfate
c(Ce(SO4)2) = 0.01 mol/L
Standard:
Pure gold
- gold, test
- cer, hydr (standardization)
Indication:
- DM140-SC at Sensor 2
Results:
Samples
Given carat value
Weight
[g]
n
24
0.023 - 0.024
18
Results
x
srel
3
23.995
0.23
0.031 - 0.033
3
17.670
0.18
14
0.040 - 0.044
4
14.098
0.13
9
0.064 - 0.067
4
9.134
0.11
Page 64/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Chemistry and Calculations
Introduction
To determine pure gold or its content in alloys we have
chosen the precipitation method with hydroquinone.
Most of the associated metals do not interfere with the
determination. As the precipitation of gold is too slow to
execute a direct titration with hydroquinone, an excess
of hydroquinone is added to the dissolved gold. The
excess is titrated back with cerium sulfate. Three individual methods are necessary for the gold determination:
• The cer method is used for the factor determination
of cerium sulfate vs. hydroquinone.
• The hydr method is used for the standardization of
these two titrants with pure gold.
• The gold method is used for the determination of
pure gold or its content in alloys.
If the gold content is unknown, the test method is
used.
The following points indicate that these methods are
suitable for the gold determination:
• The titration of hydroquinone with cerium sulfate
is reproducible (see cer method).
• It has been shown that gold solutions are very stable
over several days when kept at low pH in hydrochloric
acid (Ref. 1).
• It has been shown that copper, iron, zinc, nickel,
platinum and palladium do not interfere (Ref. 2).
We have found that also silver does not interfere.
1. Gold (Au) is oxidized to the Au3+ ion by aqua regia.
2. Au3+ is reduced by an excess of hydroquinone:
Au precipitates and quinone is formed
O
O
3. The excess of hydroquinone is then oxidized by
cerium sulfate (back titration):
O
+ 2 Ce4+
+ 2 Ce3+ + 2H+
mmol C6H6O2 dispensed (excess)
VDISP ∗ c(1/2 C6H6O2) ∗ t
mmol Au
/3 Au
1
3+
mmol Ce(SO4)2 titrated
VEQ ∗ c(Ce(SO4)2 ∗ t
mmol Au =
[VDISP ∗ c(1/2 C6H6O2) ∗ t - VEQ ∗ c(Ce(SO4)2 ∗ t]
The accuracy which can be obtained by these methods
depends on
- the quality of weighing.
- the care with which the gold sample is prepared and
dissolved.
- the amount of gold taken.
- the precision of titration.
Maintenance of the Electrode
We recommend to always clean the electrode after 6
gold titrations because gold contaminates the platinum
ring by forming a thin layer:
– Place it for two minutes in aqua regia and rinse thoroughly with deion. H2O.
(See also leaflet of the DM140-SC).
VDISP
= dispensed hydroquinone [mL]
c( /2 C6H6O2)
= hydroquinone concentration [mol/L]
VEQ
= Ce(SO4)2 consumption back titrat. [mL]
c(Ce(SO4)2)
= cerium sulfate concentration [mol/L]
1
Disposal
HCl/HNO3:
Neutralization with NaOH
Hydroquinone: Evaporate solution, special waste.
Cerium:
Precipitate with NaOH and filtrate it,
special waste.
Gold:
Filtrate solution, special waste.
Other metals: Evaporate titrated or filtrated gold
solution. Classify as special waste.
References
1. A. Chow, The Stability of Gold Solutions, Talanta 18 (1971),
453-456.
Titration Time of one Sample
Time [min]
pH ~ 1
=
2eO
Accuracy
Method
pH ~ 1
2 Au + 6H+ + 3
=
6e
2 Au3+ + 3
cer
hydr
gold
test
6
10
10-15
20-25
Electronics and electroplating applications
2. S. C. Soundar Rajan and N. Appala Raju, Titrimetic Determination
of Gold by Precipitation with Hydroquinone, Talanta 22 (1975),
185-189.
METTLER TOLEDO DL5x and DL7x Titrators Page 65/100
METTLER TOLEDO
M209
Titer determination of cerium sulfate vs. hydroquinone
Sample:
Hydroquinone solution
c(1/2 C6H6O2) = 0.05 mol/L: 1.5 mL
Compound:
Hydroquinone
M = 110.11; z = 2
Preparation:
HCl 0.1 mol/L: 40 mL
Titrant:
Cerium(IV) sulfate
c(Ce(SO4)2) = 0.01 mol/L
Preparation of the Hydroquinone Solution
– Dissolve 2.753 g hydroquinone in 900 mL deion.
H2O using a 1 L volumetric flask.
– Add 10 mL conc. H2SO4 and fill up to the mark with
deion. H2O.
Preparation of the Cerium(IV) Sulfate Solution
– Weigh in 4.043 g cerium sulfate using a glass beaker
and add 500 mL deion. H2O.
– Add 10 mL conc. H2SO4 and stir the solution while
heating it to approx. 50 °C until the sulfate is dissolved.
– Pour the solution into a 1 L volumetric flask and fill
up to the mark with deion. H2O.
Results:
Method
User
Measured
cer
Factor Ce(SO4)2/C6H4(OH)2
02-April-1993
02-April-1993
13:35
13:38
RESULTS
No
ID1
1/1
C 6H 6O 2
1/2
C 6H 6O 2
1/3
C 6H 6O 2
1/4
C 6H 6O 2
ID2
Sample amount and results
1.5
R1 = 0.98115
1.5
R1 = 0.98202
1.5
R1 = 0.98217
1.5
R1 = 0.98261
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
AUXILIARY VALUE
New value
Page 66/100 METTLER TOLEDO DL5x and DL7x Titrators
n
x
s
srel
=
=
=
=
H2 =
mL
mL
mL
mL
4
0.98199
0.000611
0.062
%
0.981989
Fixed volume U
Factor
Fixed volume U
Factor
Fixed volume U
Factor
Fixed volume U
Factor
Factor
Factor
Factor
Electronics and electroplating applications
Method "cer"
Method
cer
Version
Remarks
Factor Ce(SO4)2/C6H4(OH)2
02-April-1993 13:35
Title
Method ID . . . . . . . . . .
Title . . . . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Number samples . . . . . . . .
Titration stand . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
ID1 . . . . . . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Temperature sensor . . . . . .
Pump
Auxiliary reagent . . . . . .
Volume [mL] . . . . . . . . .
Dispense
Titrant . . . . . . . . . . .
Concentration . . . . . . . .
Volume [mL] . . . . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
Titration
Titrant . . . . . . . . . . .
Concentration [mol/L] . . . .
Sensor . . . . . . . . . . . .
Unit of meas. . . . . . . . .
Titration mode . . . . . . . .
Predespensing 1 . . . . . .
Volume [mL] . . . . . .
Titrant addition . . . . .
∆E(set) [mV] . . . . . .
Limits ∆V . . . . . . .
∆V (min) [mL] . . . .
∆V (max) [mL] . . . .
Measure mode . . . . . . .
∆E [mV] . . . . . . . .
∆t [s] . . . . . . . . .
t(min) [s] . . . . . . .
t(max) [s] . . . . . . .
Threshold . . . . . . . . .
Maximum volume [mL] . . . .
Termination after n EQPs .
n = . . . . . . . . . .
Evaluation procedure . . .
Calculation
Result name . . . . . . . . .
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Result unit . . . . . . . . .
Decimal places . . . . . . . .
Statistics
Ri (i=index) . . . . . . . . .
Standard deviation s . . . . .
Rel. standard deviation srel .
Outlier test . . . . . . . . .
Instruction
At least one solution is bad!
Please renew!
Condition . . . . . . . . . .
Condition . . . . . . . . .
Auxiliary value
ID text . . . . . . . . . . .
Formula . . . . . . . . . . .
Record
Output unit . . . . . . . . .
All results . . . . . . . . .
Table of values . . . . . . .
E - V curve . . . . . . . . .
. . . cer
. . . Factor Ce(SO4)2/C6H4(OH)2
. . . 02-April-1993 13:35
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4
Stand 1
Fixed volume U
1.5 mL
C 6H 6O 2
110.11
2
Manual
. . . HCl 0.1 mol/L
. . . 40.0
. . . 1/2 C6H6O2
. . . 0.05
. . . 1.5
. . . 50
. . . 10
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Ce(SO4)2
0.01
DM-140-SC
mV
EQP
mL
6.3
DYN
8.0
Absolute
0.01
0.2
EQU
0.5
2.0
3.0
30.0
2000.0
10.0
Yes
1
Standard
.
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. Factor
. R=VDISP*0.05/(VEQ*c)
.
.
. 5
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.
• The cerium sulfate solution is unstable because a
precipitation occurs. We recommend to prepare a
new solution every 2 days.
• The hydroquinone solution is stable but we recommend to prepare a new solution every 10 days.
Calculation
• Fixed volume U of hydroquinone =
dispensed volume VDISP = 1.5 mL
fce/hy =
• The mean value x of fce/hy is stored as auxiliary value
H2. It is used to calculate the titer of cerium sulfate
versus gold (see method "hydr").
Table of measured values
ET1
ET2
R1
Yes
Yes
Yes
. . . Factor
. . . H2=x
.
.
.
.
.
.
.
.
Printer
Yes
Yes
Yes
VEQ * c(Ce(SO4)2)
• If the mean value x of fce/hy is less than 0.9 or greater
than 1.1, then the INSTRUCTION method function
is displayed.
. . . Yes
. . . (x<0.9)?(x>1.1)
.
.
.
.
VDISP * c(1/2 C6H6O2)
EQP1
Volume
mL
Increment
mL
Signal
mV
Change
mV
1st deriv.
mV/mL
Time
min:s
0.0000
3.6000
5.4000
6.3000
6.5000
6.7000
6.9000
7.1000
7.2780
7.3990
7.4670
7.5190
7.5510
7.5760
7.5920
7.6020
7.6120
7.6220
7.6320
7.6420
7.6520
3.6000
1.8000
0.9000
0.2000
0.2000
0.2000
0.2000
0.1780
0.1210
0.0680
0.0520
0.0320
0.0250
0.0160
0.0100
0.0100
0.0100
0.0100
0.0100
0.0100
432.8
455.0
468.6
479.6
482.2
486.7
491.3
498.1
507.0
517.1
525.1
534.6
542.5
551.7
561.0
567.9
578.7
595.1
640.9
681.5
708.5
22.2
13.6
11.1
3.1
4.0
4.6
6.8
8.9
10.1
8.1
9.5
7.9
9.2
9.4
6.9
10.9
16.3
45.8
40.6
27.0
6.2
7.5
12.3
15.4
20.2
23.1
33.9
49.9
83.3
118.4
181.7
247.2
366.8
586.2
686.0
1085.0
1630.9
4585.0
4059.8
2702.0
0:30
0:57
1:16
1:31
1:40
1:49
2:04
2:19
2:37
2:54
3:10
3:27
3:44
4:07
4:24
4:41
4:58
5:18
5:39
5:53
6:13
E-V curve
Authors: MT Analytical, Application laboratory
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 67/100
METTLER TOLEDO
M210
Standardization of hydroquinone with pure gold
Sample:
Pure gold: 0.023 - 0.026 g
Instruments: - METTLER TOLEDO DL70ES/77
- METTLER balance AT261
- Printer: HP Deskjet
Compound: Gold
M = 196.97; z = 3
hydr
Method:
Preparation: Solvent mixture
conc. HCl: 5 mL / conc. HNO3: 1.5 mL
Accessories: - Two burette drives DV90
- Two 10 mL burettes DV910
- Glass beaker ME-101446
- Pump ME-65241
- Ultrasonic bath
HCl 0.1 mol/L: 40 mL
Titrant 1:
Hydroquinone
c(1/2 C6H6O2) = 0.05 mol/L
Titrant 2:
Cerium(IV) sulfate
c(Ce(SO4)2) = 0.01 mol/L
- DM140-SC at Sensor 2
Indication:
Results:
Method
User
Measured
hydr
Titer of C6H6O2, Ce(SO4)2
07-April-1993
06-April-1993
13:39
13:03
RESULTS
No
ID1
1/1
Gold
1/2
Gold
1/3
Gold
1/4
Gold
ID2
Sample amount and results
0.024295
R1 = 4.778
R2 = 0.22028
R3 = 0.99996
0.023605
R1 = 4.842
R2 = 0.21503
R3 = 0.99924
0.023662
R1 = 4.835
R2 = 0.21545
R3 = 0.99788
0.02332
R1 = 4.867
R2 = 0.21285
R3 = 0.99784
STATISTICS
Number results
R3
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
TITER
Titrant
New titer
1/2 C6H6O2
TITER
Titrant
New titer
Ce(SO4)2
n
x
s
srel
=
=
=
=
g
Weight m
mL
mmol
C 6H 6O 2
Titer
g
Weight m
mL
mmol
C 6H 6O 2
Titer
g
Weight m
mL
mmol
C 6H 6O 2
Titer
g
Weight m
mL
mmol
C 6H 6O 2
Titer
4
0.99873
0.001046
0.105
%
C 6H 6O 2
C 6H 6O 2
C 6H 6O 2
C 6H 6O 2
Titer C6H6O2
Titer C6H6O2
0.05 mol/L
t = 0.998729
0.01 mol/L
t = 1.006319
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
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [g] . . . . .
Upper limit [g] . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Pump
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Dispense
Titrant . . . . . . . . . .
Concentration . . . . . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predespensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V (min) [mL] . . .
∆V (max) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
EQP range . . . . . . . .
Limit A . . . . . . .
Limit B . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Titer
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Formula
t = . . .
Titer
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Formula
t = . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
Table of values . . . . . .
E - V curve . . . . . . . .
Auxiliary value
ID text . . . . . . . . . .
Formula . . . . . . . . . .
. . . . hydr
. . . . Titer of C6H6O2, Ce(SO4)2
. . . . 06-April-1993 13:39
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4
Stand 1
Weight m
0.023
0.026
Gold
196.967
3
Manual
. . . . HCl 0.1 mol/L
. . . . 40.0
. . . . 1/2 C6H6O2
. . . . 0.05
. . . . 1.4*H2+304.6*m
. . . . 50
. . . . 180
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R=VDISP*5/H2-C
C=m*1523*H2
mL
3
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.
Ce(SO4)2
0.01
DM140-SC
mV
EQP
mL
0.9*R
DYN
8.0
Absolute
0.01
0.2
EQU
0.5
2.0
3.0
30.0
1000.0
Yes
500
800
10.0
Yes
1
Standard
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C 6H 6O 2
R2=VDISP*0.05
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Titer C6H6O2
R3=C3/(R2-VEQ*c*H2)
C3=(m*1000*z)/M
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3
Yes
Yes
Yes
Sample Preparation
A careful sample preparation is mandatory for reproducible results.
– Weigh in a gold sample of approx. 0.025 g.
– Clean it with ethanol and let it dry - use tweezers.
– Weigh in this sample with a precision of 0.001 mg
and put it in the glass beaker.
– Add 5 mL conc. HCl and 1.5 mL conc. HNO3 (fume
hood). Never use prepared aqua regia (unstable!).
– To dissolve the gold place the beaker on a heating
plate (110 to 130 °C).
The dissolution time can be reduced by using an
ultra-sonic bath (room temperature).
– Evaporate to almost dryness (color changes from
yellow to orange), but never evaporate to complete
dryness! This would cause the reduction of gold and
give false results!
– Rinse the beaker walls with 5 mL conc. HCl and evaporate again to eliminate the nitrous compounds.
– Repeat this procedure until no yellow fumes are
formed anymore.
– Let the sample cool to room T, then titrate.
Table of measured values
Volume
mL
ET1
ET2
mmol
5
5
EQP1
Increment
mL
0.0000
2.5020
3.7530
4.3800
4.5800
4.7800
4.9800
5.1800
5.3800
5.5800
5.7800
5.9800
6.1800
6.3800
6.5800
6.7460
6.8260
6.8550
6.8700
6.8800
6.8900
6.9000
6.9100
6.9200
6.9300
6.9400
6.9500
2.5020
1.2510
0.6270
0.2000
0.2000
0.2000
0.2000
0.2000
0.2000
0.2000
0.2000
0.2000
0.2000
0.2000
0.1660
0.0800
0.0290
0.0150
0.0100
0.0100
0.0100
0.0100
0.0100
0.0100
0.0100
0.0100
Signal
mV
449.7
457.5
462.6
465.8
467.1
468.4
469.8
471.4
473.1
475.2
477.4
480.1
483.6
488.1
495.2
506.4
520.1
530.0
539.9
548.6
558.8
571.0
589.5
625.8
679.2
703.3
712.1
Change
mV
7.8
5.0
3.3
1.3
1.3
1.4
1.6
1.7
2.1
2.2
2.7
3.4
4.6
7.1
11.2
13.7
9.9
9.9
8.7
10.2
12.3
18.4
36.3
53.4
23.1
8.8
1st deriv.
mV/mL
3.1
4.0
5.2
6.3
6.7
7.0
8.1
8.4
10.5
10.9
13.7
17.2
22.8
35.3
67.5
171.5
340.3
662.6
868.0
1022.0
1225.0
1840.9
3633.0
5340.8
2408.0
882.0
Time
min:s
0:03
0:13
0:21
0:27
0:32
0:37
0:42
0:47
0:53
0:58
1:04
1:09
1:15
1:22
1:28
1:37
1:46
1:54
2:03
2:15
2.30
2:46
3:07
3:38
4:08
4:30
4:40
E-V curve
. . . . 1/2 C6H6O2
. . . . 0.05
. . . . x
. . . . Ce(SO4)2
. . . . 0.01
. . . . x*H2
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Printer
Yes
Yes
Yes
. . . . Titer of C6H6O2
. . . . H3=x
Authors: MT Analytical, Application laboratory
Electronics and electroplating applications
Other titrators
DL70ES, DL77.
Disposal
Special waste.
METTLER TOLEDO DL5x and DL7x Titrators Page 69/100
Remarks
c. Titer determination of C6H6O2 vs. gold
Calculations
thy =
a. Dispensing of hydroquinone
An excess of hydroquinone is dispensed depending
on the size of the gold sample. Furthermore, approx. 7 mL of the cerium sulfate titrant should be
consumed by the back titration. Thus the dispensed
volume of hydro-quinone (VDISP) is calculated in
the DISPENSE function.
VDISP = mL hydroquinone + mL hydroquinone
reacted with gold
=
back titrated with Ce(SO4)2
7 mL * c(Ce(SO4)2) * fce/hy
z * m * 1000
+
M * c(1/2 C6H6O2)
c(1/2 C6H6O2)
=
304.6 * m
+
1.4 * H2
The best accuracy is achieved if the consumption
of hydroquinone and cerium sulfate is less than
1 burette volume each, i.e. 10 mL. Therefore the
sample weight must lie in the range of 0.023 and
0.026 g gold. Also the titer values of both titrants
must lie in the range of 0.95 and 1.1.
b. Predispensing of cerium sulfate (back titration)
Predispensing is always applied to speed up the
titration. Here a predispensing volume of 90% of
the total cerium sulfate consumption (VEQth) is
used. This volume is calculated in the first CALCULATION function.
VEQth =
VEQth =
VDISP
fce/hy
*
c(1/2 C6H6O2)
c(Ce(SO4)2)
VDISP/H2 * 5
–
z * m * 1000
M * c(Ce(SO4)2) * fce/hy
–
z * m * 1000
M (VDISP * c(1/2 C6H6O2) – VEQ * c(Ce(SO4)2) * fce/hy)
The titer of C6H6O2 thy is stored as auxiliary value H3
for further use in the "gold" method.
d. Titer determination of Ce(SO4)2 vs. gold
The factor fce/hy was obtained by the standardization of cerium sulfate with hydroquinone (method
"cer"). The titer of cerium sulfate must be referred
to gold.
tce = thy * fce/hy = thy * H2
where
VDISP =
dispensed volume of hydroquinone
[mL]
VEQ =
cerium sulfate consumption by back
titration
VEQth =
z=
calculated cerium sulfate consumption
for back titration
equivalent number of gold = 3
m=
size of gold sample [g]
M=
molar mass of gold = 196.967
c( /2 C6H6O2)= hydroquinone concentration =
1
0.05 mol/L
c(Ce(SO4)2 =
cerium sulfate concentration =
0.01 mol/L
fce/hy =
factor of cerium sulfate vs. hydroquinone
(stored as H2)
m * 1523 * H2
Reaction Time
The complete reduction of gold with hydroquinone
takes about 2 minutes; thus the stirring time shall not
be less than 180 s.
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
M179
Sample:
Determination of the gold content in alloy
Various gold alloys with a known
(±10%) gold content
Instruments: - METTLER TOLEDO DL70ES/77
- METTLER balance AT261
- Printer: HP Deskjet
Gold, Au
M = 196.97; z = 3
Method:
0.02 - 0.08 g
Compound:
Preparation: Solvent mixture
Accessories: - Two burette drives DV90
- Two 10 mL burettes DV910
- Glass beaker ME-101446
- Pump ME-65241
- Ultrasonic bath
conc. HCl: 5 mL / conc. HNO3: 1.5 mL
HCl 0.1 mol/L: 40 mL
Titrant 1:
Hydroquinone
c(1/2 C6H6O2) = 0.05 mol/L
Titrant 2:
Cerium(IV) sulfate
c(Ce(SO4)2) = 0.01 mol/L
Method
User
Measured
- gold
- cer, hydr (standardization)
- DM140-SC at Sensor 2
Indication:
gold Purity of gold samples
08-April-1993
08-April-1993
8:48
15:36
RESULTS
No
ID1
1/1
Gold
1/2
Gold
1/3
Gold
1/4
Gold
ID2
Sample amount and results
0.024295
R1 = 38.044
R2 = 9.131
0.023605
R1 = 38.070
R2 = 9.137
0.023662
R1 = 38.108
R2 = 9.146
0.02332
R1 = 38.010
R2 = 9.123
g
Weight
%
carat
g
Weight
%
carat
g
Weight
%
carat
g
Weight
%
carat
m
purity
purity
m
purity
purity
m
purity
purity
m
purity
purity
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
n
x
s
srel
=
=
=
=
4
38.058
%
0.041247 %
0.108
%
purity
purity
STATISTICS
Number results
R2
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
n
x
s
srel
=
=
=
=
4
9.134
carat
0.009899 carat
0.108
%
purity
purity
H4
=
AUXILIARY VALUE
New VALUE
Page 72/100 METTLER TOLEDO DL5x and DL7x Titrators
0.375
Electronics and electroplating applications
Remarks
Method "gold"
Method
gold
Version
Purity of gold samples
08-April-1993
8:48
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [g] . . . . .
Upper limit [g] . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Auxiliary value
ID text . . . . . . . . . .
Formula . . . . . . . . . .
Condition . . . . . . . . .
Condition . . . . . . . .
Auxiliary value
ID text . . . . . . . . . .
Formula . . . . . . . . . .
Condition . . . . . . . . .
Condition . . . . . . . .
Pump
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Dispense
Titrant . . . . . . . . . .
Concentration . . . . . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predespensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V (min) [mL] . . .
∆V (max) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
EQP range . . . . . . . .
Limit A . . . . . . .
Limit B . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . gold
. . . . Purity of gold samples
. . . . 08-April-1993
8:48
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4
Stand 1
Weight m
0.02
0.08
Gold
196.967
3
Manual
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. H4=H1/24
. Yes
. H1<=24
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. H4=H1/100
. Yes
. (H1>24)!(H1<=100)
. . . . HCl 0.1 mol/L
. . . . 40.0
. . . . 1/2 C6H6O2
. . . . 0.05
. . . . 1.2*H2+304.6*m*H4/H3
. . . . 50
. . . . 180
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Ce(SO4)2
0.01
DM-140-SC
mV
EQP
mL
2.1
DYN
8.0
Absolute
0.02
0.2
EQU
0.5
2.0
3.0
30.0
400.0
Yes
500
700
10.0
Yes
1
Standard
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purity
R=100*(QDISP-Q)*C
C=M/(m*z*1000)
%
3
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.
purity
R2=24*(QDISP-Q)*C2
C2=M/(m*z*1000)
carat
3
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R1
Yes
Yes
Yes
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R2
Yes
Yes
Yes
. . . . Printer
. . . . Yes
Electronics and electroplating applications
• Before executing this method the carat or percent
value of the alloy has to be entered as auxiliary
value H1. If the gold content is unknown, use the
"test" method (see M180). Enter thy as H3.
• The gold concentration of the sample entered as
carat or percent is automatically transformed into
the fraction of gold and stored as H4 using the
AUXILIARY VALUE functions.
Sample Preparation
Proceed with the sample preparation as described in
method "hydr". The following remarks are important:
• Press alloys as thin as possible using a rolling device
so that the dissolution is easier.
• Use an ultrasonic bath especially for silver alloys,
be-cause silver chloride does passivate the gold
surface.
• Evaporate the aqua regia solution.
• Add 5 mL conc. HCl to the beaker and put it in the
ultrasonic bath for 5 minutes.
• Evaporate again.
• If it is not yet dissolved, repeat the procedure.
• Never evaporate to complete dryness!
Sample Weight (g)
Content (carat)
lower limit
upper limit
24
0.023
0.026
21
0.026
0.030
18
0.031
0.034
14
0.040
0.044
12
0.046
0.052
9
0.062
0.069
Dispensing of Hydroquinone
• An excess of hydroquinone is dispensed depending
on the sample size and the gold concentration.
• Furthermore, the dispensed volume (VDISP) is
calculated for a consumption of 6 mL cerium sulfate
VDISP =
=
mL hydroquinone
reacted with gold
=
z * m * Aux * 1000
M * c(1/2 C6H6O2) * thy
= 304.6 * m * H4/H3
+
mL hydroquinone back
titrated with Ce(SO4)2
+
+
6 mL * c(Ce(SO4)2) * fce/hy
c(1/2 C6H6O2)
1.2 * H2
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 be less than 180 s.
The gold content Au is:
Au = 24 * M * (QDISP – Q)
[carat]
z * 1000 * m
where
VDISP =
dispensed volume of hydroquinone
[mL]
QDISP =
dispensed amount of hydroquinone
[mmol]
Q=
cerium sulfate consumption by back
titration [mmol]
z=
equivalent number of gold = 3
m=
size of gold sample [g]
M=
molar mass of gold = 196.967
1
c( /2 C6H6O2) = hydroquinone concentration =
0.05 mol/L
c(Ce(SO4)2 = cerium sulfate concentration =
0.01 mol/L
fce/hy =
titer of cerium sulfate vs. hydroquinone
(storedas H2)
thy =
titer of hydroquinone (stored as H3)
Aux =
presumed gold content (stored as
Titration Parameters
• The titration curve may show noisy behavior in the
range of the equivalence point. This may especially
occur with samples of low gold content. In this case
we recommend to increase the minimum increment
∆V(min) to >0.02 mL.
Disposal
Special waste.
Other titrators
DL70ES, DL77.
Page 74/100 METTLER TOLEDO DL5x and DL7x Titrators
Authors: MT Analytical, Application laboratory
Electronics and electroplating applications
METTLER TOLEDO
M180
Determination of the approximate gold content content in alloys
Sample: Various gold alloys with an unknown gold
Remarks
Method "test"
With this method the gold content can be determined
within approx. 3%. The gold method can then be
executed to obtain the precise result.
content: 0.03 - 0.06 g
Method
test
Version
Approximate gold content
10-April-1993
11:09
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
tent
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [g] . . . . .
Upper limit [g] . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Pump
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Titrant addition . . . .
∆V [mL] . . . . . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
EQP range . . . . . . . .
Limit A . . . . . . .
Limit B . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Auxiliary value
ID text . . . . . . . . . .
Formula . . . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V (min) [mL] . . .
∆V (max) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
EQP range . . . . . . . .
Limit A . . . . . . .
Limit B . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Output unit . . . . . . . .
. . . . test
. . . . Approximate gold con. . . . 10-April-1993
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11:09
1
Stand 1
Weight m
0.03
0.06
Gold
196.967
3
Manual
1st TITRATION function: The gold reduction with
hydroqui-none is done by a titration in order
• to determine the total amount of C6H6O2 dispensed
and
• to obtain an excess of at least 1 mL C6H6O2 (titrant
addi-tion ∆V = 0.5 mL).
Titration Curve: Gold Reduction with Hydroquinone
. . . . HCl 0.1 mol/L
. . . . 40.0
. . . . 50
. . . . 10
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1/2 C6H6O2
0.05
DM-140-SC
mV
EQP
INC
0.5
EQU
0.5
2.0
10.0
40.0
200.0
Yes
800
500
20.0
Yes
1
Standard
. . . . Amount of C6H6O2
. . . . H5=Q+QEX
. . . . 50
. . . . 120
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Ce(SO4)2
0.01
DM-140-SC
mV
EQP
DYN
8.0
Absolute
0.02
0.2
EQU
0.5
2.0
3.0
30.0
400.0
Yes
500
700
10.0
Yes
1
Standard
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content
R=100*(H5-Q[2])*C
C=M/(m*z*1000)
%
1
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content
R2=24*(H5-Q[2])*C2
C2=M/(m*z*1000)
carat
1
. . . . Printer
Electronics and electroplating applications
The total amount of C6H6O2 dispensed is stored as
auxiliary value H5.
2nd TITRATION function: The excess of hydroquinone
is titrated back with cerium sulfate.
Titration Curve: Back Titration with Cerium Sulfate
Disposal
Special waste.
Authors: MT Analytical, Application laboratory
METTLER TOLEDO DL5x and DL7x Titrators Page 75/100
METTLER TOLEDO
M192
Determination of lead(IV) in batteries
Sample:
Lead for batteries (PbO2: 8-30%)
0.5 - 1 g
Substance:
Lead, Pb4+ as lead oxide, PbO2
M = 239.2, z = 2
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Preparation: 30% HNO3 , 15 mL
10% H2O2 , 5 mL
Hot deioniezd water, 30 mL.
Titrant:
Potassium permanganate, KMnO4
c(1/5 KMnO4) = 0.1 mol/L
Standard:
Di-sodium oxalate, Na2C2O4
(see application M527)
Results:
40006
Accessories: Glass titration beakers
ME-101446
Indication:
DM140
PbO2
n
Comments
Mean value
8.5547 %
5
DL40 application no. 305
Theoretical
content
8-10 %
Rel. standard
deviation srel
0.33 %
Mean value
32.64 %
Theoretical
content
30 ± 3 %
Sample size : 0.5 g
Rel. standard
deviation srel
0.48 %
Consumption: 12 mL
Mean value
2.84 mmol
Theoretical
content
0
Rel. standard
0.48 %
Sample size: 1 g
Consumption: 20 mL
5
4
DL40 application no. 305
DL40 application no. 305
Blank value
Consumption: 27.5 mL
Page 76/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
40006
Version
PbO2
19-01-2001
Remarks
• The method was developed on the DL40 titrator
17:32
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . 40006
. . . PbO2
. . . 19-01-2001
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17:32
Lead in batteries
Weight
0.5
1.5
239.2
2
Stand 1
Manual
. . . 50
. . . 10
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1/5 KMnO4
0.1
DM140
mV
No
Dynamic
8.0
0.02
0.2
Equilibrium controlled
2.0
1.0
5.0
30.0
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300
No
No
Positive
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30.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=(H4-Q)*C/m
C=M/(10*z)
4
%
Pb content
Yes
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R2=VEQ
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. 0
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. No
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3
mL
Consumption
Yes
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
and has been adapted for the DL5x- and DL7xtitrators.
• The Pb(IV) content is expressed as PbO2 and is
detemined by back titration after addition of excess
hydrogen peroxide solution.
Sample preparation
1) Dissolve the sample in a glass titration beaker by
adding 15 mL of 30% nitric acid HNO3. Stir the
solution until all red traces are dissolved.
2) 5 mL 10% hydrogen peroxide solution are added
by using the dispensing function of the titrator.
Pb(IV) is reduced to Pb(II) by H2O2:
Pb4+ + H2O2 = Pb2+ + O2 + 2 H+ (z = 2)
Pb4+ + 2 e-
= Pb2+
3) 30 mL hot deionized water are added and stir to
achieve complete solvation.
Procedure
1) The exact concentration of the H2O2-solution is
determined by performing a blank titration using
a similar method as for the sample determination.
The blank value is stored as auxiliary value H4
(mmol).
2) Pb(IV) is then determined by a back-titration of
excess H2O2 using potassium permanganate as a
titrant:
2MnO4 - + 5 Η2Ο2 + 6 H+ =
2Mn2+ + 5O2 + 8Η2O
(z =2)
Literature
•
DL40 application no. 305
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Electronics and electroplating applications
Authors: MT Analytical, Application laboratory
METTLER TOLEDO DL5x and DL7x Titrators Page 77/100
METTLER TOLEDO
M193
Complexometric titration of lead in alloy
Sample:
Lead-tin-antimony alloy,
10 mL aliquots
Substance:
Lead, Pb2+
M = 207.2, z = 1
Instruments: METTLER TOLEDO DL53
Rondo 60 sample changer
Olivetti ArtJet 20
Preparation: 50 mL deion. water
Titrant:
Standard:
EDTA
c(EDTA) = 0.1 mol/L
Zinc sulphate, ZnSO4
(see application M528)
Method:
40007
Accessories:
Glass titration beakers
ME-101446
Indication:
DP550 Phototrode with
DIN-Lemo adapter ME-89600
Results:
Mean value
Pb2+
n
Comments
45.49 %
5
DL40 application no. 406
Consumption: 1.7 mL
Rel. standard
deviation srel
0.34 %
Mean value
98.13 %
Rel. standard
deviation srel
0.21 %
5
DL40 application no. 403
Test with Pb((NO3)2 standard
Preparation:
1. use buffer solution pH 5.4
2. Indicator: xylenol orange
3. Sensor: DP550
4. Titrant: 0.1 ml/L EDTA
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
Method
40007
Version
Remarks
Pb2+
22-01-2001
Title
Method ID . . . . . . .
Title
. . . . . . .
Date/time . . . . . . .
Sample
Sample ID . . . . . . .
Entry type . . . . . . .
Volume [mL] . . . . .
Molar mass M . . . . . .
Equivalent number z . .
Titration stand . . . .
Pump . . . . . . . .
Rinse . . . . . . . .
Solvent . . . . .
Volume
. . . . .
Conditioning . . . .
Temperature sensor . . .
Stir
Speed [%] . . . . . . .
Time [s] . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . .
Concentration [mol/L]
Sensor . . . . . . .
Unit of meas. . . . .
Predispensing . . . . .
Titrant addition . . . .
∆V [mL] . . . . . . .
• The method was developed on the DL40 titrator
10:47
. . . . . . 40007
. . . . . . Pb2+
. . . . . . 22-01-2001
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10:47
Pb/Sn/Sb alloy
Fixed volume
10.0
207.2
1
ST20A
No
Yes
H 2O
20.0
No
Manual
. . . . . . 50
. . . . . . 10
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EDTA
0.1
DP550
mV
No
Incremental
0.05
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
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Equilibrium controlled
0.5
2.0
5.0
30.0
.
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300
No
No
Positive
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5.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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.
R=Q*C/m
C=M/(10*z)
2
%
Pb content
Yes
.
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.
R2=VEQ
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. 0
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.
3
mL
Consumption
Yes
Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
and has been adapted for the DL5x- and DL7xtitrators.
• The Pb(II) content is detemined by complexometric
titration with EDTA.
Sample preparation
1) Dissolve 1-1.5 g of the finely pulverized alloy in a
250 mL beaker.
2) Add 20 mL 1:1 HCl and heat
3) To the hot solution add 10 mL of 1.1 HNO3, heat
until dissolution is complete.
4) Add 20 mL of 4% KCl, 50 mL of 1.1 HCl, 50 mL
deion. water and 20 mL 20% tartaric acid solution.
5) Boil 2 minutes.
6) Cool to room temperature.
7) Add 5 drops of 0.2% aqueous solution of xylenol
orange and 30% hexamethylene tetramine until the
solution turns red (for this sample size you need
about 35 mL).
8) Dilute to 200 mL with 1:1 HCl.
9) Take aliquots of 10 mL.
Procedure
1) This procedure is only suitable for the determination of Pb in Pb/Sn/Sb alloy. The alloy is dissolved
due to the formation in a strong acid medium of a
soluble chloro-plumbate complex.
2) The solution is diluted to volume using 1:1 HCl
since no precipitate is formed at high concentration
of HCl.
3) Sn and Sb are masked by tartaric acid. Pb can be
directly determined by titration with EDTA:
Pb2+ + H2-EDTA2- = Pb-EDTA2- + 2 H+
The colour change at the equivalence point turns
from red to yellow.
Literature
•
DL40 application no. 406
•
Application no. M528 in Application brochure18,
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Electronics and electroplating applications
Authors: MT Analytical, Application laboratory
METTLER TOLEDO DL5x and DL7x Titrators Page 79/100
METTLER TOLEDO
M194
Determination of nickel in an electroplating bath
Sample:
Nickel bath, 0.5 mL
Substance:
Nickel as NiSO4,
M = 262.7 g/mol, z = 1
Instruments: METTLER TOLEDO DL70
METTLER TOLEDO ST20A
METTLER TOLEDO AT261
Matrix Printer Epson LX800
with serial interface 8148
Preparation: Deionised water, 50 mL
Buffer pH 10, 10 mL
0.5 g Murexide/NaCl 1:200 trituration.
Titrant:
EDTA, c(EDTA) = 0.1 mol/L
Standard:
Zinc sulfate, c(ZnSO4) = 0.1 mol/L
(See METTLER method M007)
Results:
Method:
vd01
Accessories: Titration beakers ME-101974
2 peristaltic pumps ME-65241
Indication:
vd01 Nickel in Galvanic Bath
19-Dec-1989 15:22
SW Version 1.2
measured
Titrator
User
DP550 Phototrode at sensor 2
with DIN-Lemo adapter
ME-89600
19-Dec-1989
15:50
Mettler Tiel
J.v.d.Ouweland
RESULTS
No
1/1
1/2
1/3
1/4
1/5
1/6
1/7
1/8
Identification
Volume
0.5
0.5
0.5
0.5
0.5
0.5
0.5
0.5
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Page 80/100 METTLER TOLEDO DL5x and DL7x Titrators
Results
mL
mL
mL
mL
mL
mL
mL
mL
n
x
s
srel
82.35
82.59
82.38
82.07
82.14
82.75
82.48
82.31
g/L
g/L
g/L
g/L
g/L
g/L
g/L
g/L
= 8
= 82.39
= 0.225
= 0.273
g/L
g/L
%
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
NiSO4.6H2O
Electronics and electroplating applications
Method
Method
vd01
Version
Nickel in Galvanic Bath
13-Sep-1991 15:22
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples
. . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Pump
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Pump
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor
. . . . . . . . . .
Unit of meas . . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set)[mV] . . . . .
Limits ∆V . . . . . .
∆V(min) . . . . . .
∆V(max) . . . . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold
. . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Record
Short-form method . . . . .
All results . . . . . . . .
Table of measured values . .
E - V curve . . . . . . . .
. . . . vd01
. . . . Nickel in Galvanic Bath
. . . . 13-Sep-1991 15:22
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8
ST20
Fixed volume U
0.5
262.7
1
. . . . H 2O
. . . . 10.0
. . . . Buffer 10
. . . . 10.0
. . . . 50
. . . . 10
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EDTA
0.1
DP550
As installed
EQP
mL
0.5
DYN
8.0
Absolute
0.02
0.1
EQU
1.0
1.0
3.0
30.0
10.0
15.0
Yes
1
Standard
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NiSO4.6H2O
R=Q*C/U
C=M/z
g/L
2
Remarks
• The Ni(II) content is detemined by complexometric
titration with EDTA. Murexide is used as indicator,
and the colour change is monitored by a DP550
phototrode.
Sample preparation
1) Add the mureide indicator to the sample
2) The addition of water and buffer is performed automatically by two peristaltic pumps.
Procedure
• Nickel ions forms a yellow complex with murexide
in alkaline solution:
Ni 2+ + Murexide - → Ni-Murexid+
Ni forms a more stable complex with EDTA:
Ni-Murexid+ + EDTA 4- → Ni-EDTA2-+ MurexideAt the equivalence point, Ni(II) has been complexed by EDTA and murexide is free in the alkaline solution. There is a colour change from yellow
to blue-violet.
• The shape of the titration curve is somewhat affected by the concentration of the indicator. The
results, however, do not differ significantly.
Chemicals
. . . . H 2O
. . . . 10.0
• Buffer solution pH 10: 570 mL 25% NH3 and
. . . . R1
. . . . Yes
. . . . Yes
Table of mesured values and E-V curve
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Yes
Yes
Yes
Yes
Literature
1. METTLER TOLEDO DL70 Applications Brochure 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.
Electronics and electroplating applications
Author:
J. v.d. Ouweland, MT-NL
METTLER TOLEDO DL5x and DL7x Titrators Page 81/100
METTLER TOLEDO
M195
Determination of silver in silver alloy
Sample:
Silver, silver alloys
approx. 0.04 g
Compound:
Silver, Ag
M = 107.868; z = 1
Instruments: METTLER TOLEDO DL70
METTLER TOLEDO microbalance MT5
Printer: EPSON FX800
Method:
Preparation: Deion. H2O, 50 mL
HNO3 33%, 3 mL
Titrant:
Sodium chloride
c(NaCl) = 0.1 mol/L
Standard:
Silver nitrate, AgNO3
(see application M536)
Ag02
Accessories: Glass titration beaker ME-101446
Indication:
DM141-SC at Sensor 2
Results:
AgO2 Purity of AgNO3
23-04-1990 10:51
SW Version 1.2
measured
Titrator
User
23-04-1990
11:53
rvr
RESULTS
No
1/1
1/2
1/3
1/4
1/5
Identification
Ag
Ag
Ag
Ag
Ag
Alloy
Alloy
Alloy
Alloy
Alloy
Weight
0.051274
0.051274
0.051274
0.051274
0.051274
STATISTICS
Number results
R1
Mean value
Standard deviation
Rel. standard deviation
Outlier test: no outliers!
Page 82/100 METTLER TOLEDO DL5x and DL7x Titrators
Results
g
g
g
g
g
n
x
s
srel
94.9658
94.9658
94.9658
94.9658
94.9658
=
=
=
=
%
%
%
%
%
5
94.9922 %
0.01715 %
0.018
%
Silver
Silver
Silver
Silver
Silver
Silver
Silver
Electronics and electroplating applications
Method
Method
AgO2
Version
Remarks
Sample Preparation
Purity of AgNO3
23-04-1990 10:51
Title
Method ID . . . . . . . . .
Title . . . . . . . . . . .
Date/time . . . . . . . . .
Sample
Number samples . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Lower limit [g] . . . . .
Upper limit [g] . . . . .
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Metered amount [%] . .
Nominal content [%] .
Conversion const. . .
Titrant addition . . . .
∆V [mL] . . . . . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s] . . . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Result unit . . . . . . . .
Decimal places . . . . . . .
Record
Raw results . . . . . . . .
Table of measured values . .
E - V curve . . . . . . . .
Statistics
Ri (i 0 index) . . . . . . .
Standard deviation s . . . .
Rel. standard deviation srel
Outlier test . . . . . . . .
Record
All results . . . . . . . .
. . . . AgO2
. . . . Purity of AgNO3
. . . . 23-04-1990 10:51
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3
Stand 1
Weight m
0.03
0.07
Ag Alloy
107.868
1
. . . . 60
. . . . 5
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NaCl
0.1
DM-141-SC
mV
EQP
% nominal content
95.0
95.0
M/(10*z)
INC
0.05
EQU
0.5
2.0
3.0
15.0
500.0
10.0
Yes
1
Standard
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Silver
R=Q*C/m
C=M/(10*z)
%
4
. . . . Yes
. . . . Yes
. . . . Yes
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R1
Yes
Yes
Yes
– Clean the sample with acetone and let it dry – use
tweezers.
– Weigh in a sample corresponding to approx. 40 mg
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 wa-ter bath until the sample is completely dissolved.
– Let the sample cool down to room temperature and
add 50 mL deion. H2O.
This procedure is prerequisite to achieve high precision.
High Precision
Method and preparation are designed for highest precision, i.e. RSD better than 0.050%. Our example shows
a reproducibility of 0.018% RSD. This high precision is
required, for example, by mint companies or electronic
circuitry manufacturers.
High Speed
The method was also streamlined to fast titrations.
Table of measured values
Volume
mL
E1
E2
EQP1
. . . . Yes
0.000
2.223
3.335
3.891
3.941
3.991
4.041
4.091
4.141
4.191
4.241
Increment
mL
2.223
1.112
0.556
0.050
0.050
0.050
0.050
0.050
0.050
0.050
Signal
mV
215.9
197.4
175.0
140.5
134.7
126.5
111.0
75.6
31.0
15.0
5.4
Change
mV
-18.5
-22.4
-34.5
-5.8
-8.2
-15.5
-35.5
-44.6
-16.0
-9.6
1st deriv. Time
mV/mL
min:s
-8.3
-20.2
-62.0
-115.6
-163.5
-309.7
-709.2
-891.8
-319.5
-192.1
0:03
0:13
0:21
0:29
0:34
0:40
0:46
0:53
0:59
1:04
1:10
E-V curve
Literature
3. METTLER TOLEDO Application No. M536
(appl. brochure no. 18).
Disposal
Silver precipitate can be separated. The filtrated solution is neutralized with NaOH.
Other titrators
DL50 Graphix, DL53/55 (use standard methods)
DL58, DL77.
Electronics and electroplating applications
Author:
Ruth von Rotz, Application Laboratory MT
METTLER TOLEDO DL5x and DL7x Titrators Page 83/100
METTLER TOLEDO
M196
Determination of free potassium cyanide in a silver bath
Sample:
Copper bath, 1 mL
Substance:
Potassium cyanide, KCN
M = 65.12, z = 1
Instruments: METTLER TOLEDO DL67
METTLER TOLEDO ST20A
Matrix printer Epson LX800
with serial inteface 8148
AT261
Preparation: 50 mL deion. water
Titrant:
Silver nitrate, AgNO3
c(AgNO3) = 0.1 mol/L
Standard:
Sodium chloride
(see application M525)
Method:
BL20
Accessories: Titration beakers ME-101974
Peristaltic pump SP40
Indication:
DM141-SC
Results:
Method
User
Measured
BL20 KCN im cy.Ag.Bad
24-02-1994
17-02-1994
10:46
14:49
RESULTS
No
ID1
ID2
Sample amount and results
1/1
R1 =
R2 =
1/2
R1 =
R2 =
1/3
STATISTICS
Number results
Mean value
R1 =
R2 =
R1
Page 84/100 METTLER TOLEDO DL5x and DL7x Titrators
1.0
110.34
8.49
1.0
111.64
8.59
1.0
114.09
8.78
mL Fixed volume U
g/L
KCN
mL
Verbrauch
mL Fixed volume U
g/L
KCN
mL
Verbrauch
mL Fixed volume U
g/L
KCN
mL
Verbrauch
n = 3
x = 112.02
g/L
KCN
Electronics and electroplating applications
Method
Method
Remarks
BL20
Version
KCN im cy.Ag.Bad
17-02-1994 10:46
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Sample no. . . . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
EQP titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [mL] . . .
∆V(max) [mL] . . .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Calculation
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Decimal places . . . . . . .
Result unit . . . . . . . .
Result name . . . . . . . .
Statistics . . . . . . . . .
Calculation
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Decimal places . . . . . . .
Result unit . . . . . . . .
Result name . . . . . . . .
Statistics . . . . . . . . .
Statistik
Ri (i=Index) . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
Sample preparation
. . . . BL20
. . . . KCN im cy.Ag.Bad
. . . . 17-02-1994 10:46
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20
ST20 1
Fixed volume
1.0
65.12
1
Manual
. . . . 50
. . . . 10
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AgNO3
0.1
DM141-SC
mV
EQP
to volume
1
DYN
8.0
Absolute
0.05
0.5
EQU
0.5
1.0
3.0
30.0
50.0
30.0
Yes
1
Standard
1) 1 mL silver bath is diluted with 50 mL deionized water
Reaction
•
Ag+ + 2 CN- = Ag(CN)2 As long as free cyanide is still present, the solution remains clear, but the first excess of silver
causes formation of a white solid that mark the
endpoint:
Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
•
. . . . H 2O
. . . . 10.0
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R=Q*C/m
C=M*2
2
g/L
KCN
Yes
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R2=VEQ
A soluble complex Ag(CN)2 - is first formed by
the reaction between silver and cyanide ion:
since 1 mol of Ag ions reacts with two moles of
cyanides, the factor 2 is taken into account in
the calculation.
E-V curve
2
mL
Verbrauch
Yes
. . . . R1
. . . . Printer
. . . . Yes
Literature
•
•
•
Disposal
Cyanide waste
Other titrators
•
Application note, DL25 Application Brochure
"Petroleum and electroplating", ME-51724627.
Vogel's textbook of quantitative inorganic
analysis, 4th edition, Longman Group Limited ,
1978.
D.A. Skoog, D.M. West, "Fundamentals of Analytical Chemistry", Holt, Rinehart, and Winston,
1969.
Application no. M525 in Application brochure18,
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
M197
Titration of Tin(II) in acidic tin bath
Sample:
Acidic tin bath, 2 mL
Substance:
Tin(II), Sn2+
M = 118.71, z = 2
Instruments: METTLER TOLEDO DL67
METTLER TOLEDO ST20A
Matrix printer Epson LX800
with serial inteface 8148
AT261
Preparation: 50 mL deion. water
BL70
Method:
Titrant:
Iodine, I2
c(1/2 I2) = 0.1 mol/L
Standard:
Arsenic trioxide, As2O3
(see application M016)
Accessories: Titration beakers ME-101974
Peristaltic pump SP40
DM140-SC
Indication:
Results:
Method
User
Measured
BL70 Sn-(II) im sauren Sn-Bad
21-02-1994
21-02-1994
16:09
16:18
RESULTS
No
ID1
ID2
Sample amount and results
1/1
2.0
R1 = 21.34
2.0
R1 = 17.79
2.0
R1 = 17.59
1/2
1/3
STATISTICS
Number results
Mean value
R1
Page 86/100 METTLER TOLEDO DL5x and DL7x Titrators
mL Fixed volume U
g/L
mL Fixed volume U
g/L
mL Fixed volume U
g/L
n = 3
x = 18.91
g/L
Electronics and electroplating applications
Method
Method
Remarks
BL70
Version
Sn-(II) im sauren Sn-Bad
21-02-1994 16:09
Title
Method ID . . . . . . . . .
Title
. . . . . . . . .
Date/time . . . . . . . . .
Sample
Sample no. . . . . . . . . .
Titration stand . . . . . .
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
Molar mass M . . . . . . . .
Equivalent number z . . . .
Temperature sensor . . . . .
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
EQP titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
Titration mode . . . . . . .
Predispensing 1 . . . . .
Volume [mL] . . . . .
Titrant addition . . . .
∆E(set) [mV] . . . . .
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
∆V(max) [%buVol] .
Measure mode . . . . . .
∆E [mV] . . . . . . .
∆t [s]
. . . . . . .
t(min) [s] . . . . . .
t(max) [s] . . . . . .
Threshold . . . . . . . .
Maximum volume [mL] . . .
Termination after n EQPs
n = . . . . . . . . .
Evaluation procedure . .
Calculation
Formula . . . . . . . . . .
Constant . . . . . . . . . .
Decimal places . . . . . . .
Result unit . . . . . . . .
Result name . . . . . . . .
Statistics . . . . . . . . .
Rinse
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
Statistik
Ri (i=Index) . . . . . . . .
Record
Output unit . . . . . . . .
All results . . . . . . . .
. . . . BL70
. . . . KCN im cy.Ag.Bad
. . . . 21-02-1994 16:09
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20
ST20 1
Fixed volume
2.0
118.71
2
Manual
. . . . 50
. . . . 10
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1/2 I2
0.1
DM140-SC
mV
EQP
to volume
0
DYN
8.0
Relative
0.5
5.0
EQU
0.5
1.0
2.0
20.0
100.0
50.0
Yes
1
Standard
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R=Q*C/m
C=M/z
2
g/L
Sn2+
Yes
Sample preparation
1) 2 mL acidic silver bath is diluted with 50 mL
deionized water.
Reaction
•
Stannous tin Sn(II) is converted quantitatively
into stannic tin Sn(IV) by titration with iodine
in the presence of hydrochloric acid:
SnCl2 + 2HCl + I2 =
SnCl4 + 2 HI
where
Sn2+
I2
+
•
•
=
2e =
Sn4+ + 2 e2 I-
Sn(II) is oxidized to Sn(IV) by iodine, and iodine
is reduced to iodide.
Hydrochloric acid must be present in order to
supply chloride ions for the oxidation, otherwise
the readily hydrolysed Sn(SO4)2 is produced. If
necessary, add 5 mL concentrated HCl.
. . . . H 2O
. . . . 10.0
. . . . R1
. . . . Printer
. . . . Yes
Application note
•
Potassium iodate can be used instead of iodine to
titrate the sample:
IO3- + 2Sn2+ + 6H+ + Cl- = ICl + 2Sn4+ + 3H2O
KIO3 is standardized with sodium thiosulphate
Na2S2O3 (see application M526).
Disposal
CAUTION: arsenic trioxide is very poisonous!
Special waste
Other titrators
Literature
•
•
•
Application note, MT Germany, in application
brochure "Galvanik", 1995.
K.E. Langford, J.E. Parker, "Analysis of electroplating and related solutions", 4th edition, Robert
Draper Ltd. , 1971.
Application no. M016, Application brochure 9,
"Standardization of Titrants II" ME-51724652,
1994.
DL50 Graphix
DL53/DL55/DL58
DL70ES, DL77.
Author: Application laboratory, MT Germany
Electronics and electroplating applications
METTLER TOLEDO DL5x and DL7x Titrators Page 87/100
METTLER TOLEDO
M198
Photometric titration of zinc in a spin bath
Sample:
Spin-bath, 5 mL
Substance:
Zn2+ , M = 161.4, z = 1
ZnSO4 , M = 65.37, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Preparation: 10 mL deionized water
50 mL buffer pH 4.5
30 mg Xylenol orange
Titrant:
EDTA,
c(EDTA) = 0.1 mol/L
Standard:
Zinc sulphate, ZnSO4
(see appl. M528)
40008
Accessories: Titration beakers ME-101974
Indication:
DP550 Phototrode with
DIN-Lemo adapter ME-89600
30 mg Xylenol orange.
Results:
Mean value
Results
n
Comments
ZnSO4:
7.9824 g/L
5
DL40 application no. 84-22
SO42- :
4.7875 g/L
Rel. standard
deviation srel
0.39 %
Page 88/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Method
Method
40008
Version
Remarks
ZnSO4 in spin-bath
24-01-2001 11:15
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
• The method was developed on the DL40 titrator
and has been adapted for the DL5x- and DL7xtitrators.
. . . 40008
. . . ZnSO4 in spin-bath
. . . 24-01-2001 11:15
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Spin bath
Fixed volume
5.0
161.4
1
Stand 1
Manual
. . . 50
. . . 15
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EDTA
0.1
DP550
mV
No
Incremental
0.1
Equilibrium controlled
1.0
2.0
5.0
30.0
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200
No
No
Positive
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=Q*C/m
C=M/z
4
g/L
ZnSO4 Bath cont.
Yes
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R2=Q*C2/m
C2=96.01/z
4
g/L
SO42- in sample
Yes
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R3=VEQ
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
• Adjust the DP 550 at 1000 mV in deionised water
before starting titration (100% transmission).
Sample preparation
1) 5 mL spin bath are diluted in a titration beaker
by adding 10 mL deionized water.
2) 50 mL buffer solution pH 4.5 are added
3) 30 mg Xylenol orange are added to the sample
solution.
Reaction
• Zinc ions form a red complex with xylenol orange
in acidic solution:
Zn2+ + Xylenol 2- → Zn-Xylenol
By adding EDTA during titration, Zn forms a more
stable complex with EDTA:
Zn-Xylenol + EDTA 4- → Zn-EDTA + Xylenol 2At the equivalence point, all Zn ions have been
complexed by EDTA and xylenol orange is free in
the acidic solution. There is a colour change from
red to yellow.
Chemicals
•
4
mL
Consumption
No
Buffer solution pH 4.5:
60 mL glacial acetic acid and 50 g sodium acetateare dissolved in a 1 L volumetric flask. Dilute
to the mark with deionized water.
Literature
•
•
DL40 application note no. 84-22
Applications no. M528 in Application brochure18, "Standardization of Titrants", 2000.
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.
Electronics and electroplating applications
Authors: Application Laboratoy MT-ANA
METTLER TOLEDO DL5x and DL7x Titrators Page 89/100
METTLER TOLEDO
M199
Determination of sulphate in a spin bath by precipitation titration
Sample:
Diluted spin-bath, (1:100)
Aliquot 1 mL
Substance:
SO42- , M = 96.01, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Method:
Preparation: 20 mL deionized water
30 mL acetone
1 mL mixed indicator
Titrant:
Barium perchlorate, Ba(ClO4)2
c(Ba(ClO4)2) = 0.005 mol/L
Standard:
EDTA
(see appl. M540)
40009
Accessories: Titration beakers ME-101974
Indication:
DP550 Phototrode with
DIN-Lemo adapter ME-89600
1 mL mixed indicator.
Results:
Results
n
Comments
Mean value
SO42- :
332.78 g/L
5
DL40 application no. 84-222
Rel. standard
deviation srel
0.20 %
Mean value
SO42- :
2.9766 g/L
7
Rel. standard
deviation srel
0.26 %
DL40 application no. 106
The brine contained 300 g/L
i.e. more than 100 times the
molar sulphate concentration
Standardization:
Use 5 mL ZnSO4 0.005 mol/L
in 5 mL 0.5 mol/L NaCl to
reproduce the same matrix
effects as in the sample
Page 90/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Remarks
Method
Method
40009
Version
SO42- in spin-bath
24-01-2001 16:30
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait [s] . . . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
• The method was developed on the DL40 titrator
and has been adapted for the DL5x- and DL7xtitrators.
. . . 40009
. . . SO42- in spin-bath
. . . 24-01-2001 16:30
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Spin bath
Fixed volume
1.0
96.01
1
Stand 1
Manual
. . . 50
. . . 30
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Ba(ClO4)2
0.005
DP550
mV
Yes
3.0
20
Incremental
0.1
Equilibrium controlled
2.0
10.0
10.0
45.0
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100
No
No
Negative
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=Q*C/m
C=M/z
2
g/L
SO42- sample
Yes
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R2=Q*100
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R3=VEQ
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
2
g/L
SO42- bath
Yes
4
mL
Consumption
No
Disposal
• Adjust the DP 550 at 1000 mV in deionised water
before starting titration (100% transmission).
Sample preparation
1) 1 mL spin bath are diluted in a 100 mL volumetric
flask by adding deionized water.
2) 1 mL aliquot is taken and added to the titration
beaker.
3) 20 mL deionized water are added.
4) Add 30 mL acetone.
Steps 3+4: The aqueous mixture is prepared in advance and degassed in an ultrasonic bath before
use. 50 mL are then added to the sample.
5) If necessary, acidify the sample to pH 3-6 with
aqueous perchloric acid 0.05 mol/L.
6) 1 mL mixed indicator is added to the sample prior
titration.
Reaction
• Sulphate SO42- is determined by precipitation titration with barium perchlorate:
SO42- + Ba2+ → BaSO4
• For a better recognition of the endpoint an indicator
is added to the sample solution.
Chemicals
•
Mixed indicator:
In a 50 mL volumetric flask 0.12 mL 1.6% methylene blue solution and 50 mg Thorin are dissolved
in 5 mL 0.1 mol/L hydrochloric acid. Fill up to the
mark with deionized water.
Literature
•
•
•
DL40 application note no. 84-22
DL40 application no. 106
Applications no. M528 in Application brochure18, "Standardization of Titrants", 2000.
Special waste).
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Electronics and electroplating applications
Authors: Application laboratoy MT-ANA
METTLER TOLEDO DL5x and DL7x Titrators Page 91/100
METTLER TOLEDO
M200
Titration of fluoride in soldering salts
Sample:
Soldering salts, 1 g
Substance:
F - , M = 18.998, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Preparation: 150 mL deionized water
heat at 50°C, 10 minutes
10 mL buffer pH 6
Titrant:
Lanthanum nitrate, La(NO3)3
c(1/3 La(NO3)3 ) = 0.1 mol/L
Standard:
Sodium fluoride, NaF
Method:
40010
Accessories: 250 mL titration beakers
ME-23829
Indication:
DX219 Fluoride ISE
DX200 Reference electrode
(Bridge electrolyte:
1 mol/L KNO3)
Results:
Results
n
Comments
Mean value
F- :
2.17 %
4
DL40 application note
no. 8317
Rel. standard
deviation srel
0.20 %
Page 92/100 METTLER TOLEDO DL5x and DL7x Titrators
Electronics and electroplating applications
Remarks
Method
Method
40010
Version
F- soldering salts
24-01-2001 16:30
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Lower limit [g] . . . . . .
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
• The method was developed on the DL40 titrator
. . . 40010
. . . F- soldering salts
. . . 24-01-2001 16:30
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Soldering salts
Weight
0.8
1.2
18.998
1
Stand 1
Manual
. . . 50
. . . 30
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1/3 La(NO3)3
0.1
DX219
mV
No
Incremental
0.2
Equilibrium controlled
1.0
3.0
5.0
45.0
.
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200
No
No
Positive
.
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=Q*C/m
C=M/(10*z)
2
%
% FYes
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R2=Q*C2
C2=M*1000/z
2
mg
F- sample
Yes
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R3=VEQ
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
4
mL
Consumption
No
and has been adapted for the DL5x- and DL7xtitrators.
Sample preparation
1) Approx. 1 g soldering salts are dissolved in 150 mL
deionized water .
2) The sample solution is heated at 50°C under stirring during 10 minutes.
3) After cooling to room temperature, 10 mL buffer
pH 6 are added before titration.
Reaction
• Fluoride is precipitated by lanthanum in a slightly
acid solution:
3 F- + La3+ = LaF3
• 1 mol of La3+ ions reacts with 3 mol of fluoride
ions
Chemicals
• Buffer pH 6 solution:
Dissolve approx. 85 g sodium acetate in 1 L deionized water. While monitoring the pH value, slowly
add glacial acetic acid to achieve pH 6.
• Titrant solution :
Dissolve 14.44 g La(NO3)3 • 6H2O in a 1 L volumetric flask and fill up to the mark to obtain the
concentration c( 1/3 La(NO3)3 ) = 0.1 mol/L.
Literature
• DL40 application note no. 8317
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Electronics and electroplating applications
Authors: Application Laboratory MT-ANA
METTLER TOLEDO DL5x and DL7x Titrators Page 93/100
METTLER TOLEDO
M201
Standardization of 1/2 Pb(NO3)2
Sample:
NaF 0.1 mol/L standard solution,
5 mL
Substance:
F - , M = 18.998, z = 1
Instruments: METTLER TOLEDO DL53
Matrix printer Epson LX800
with serial inteface 8148
AT261
Preparation: 20 mL deionized water
20 mL ispropanol
10 mL buffer pH 6
Titrant:
Lead nitrate, Pb(NO3)2
c( 1/2 Pb(NO3)2 ) = 0.1 mol/L
Standard:
--
Method:
40011
Accessories: Titration beaker ME-101974
Indication:
DX219 Fluoride ISE
DX200 Reference electrode
(Bridge electrolyte:
1 mol/L KNO3)
Results:
Results
n
Comments
Mean value
Titer :
0.97892
6
DL40 application
Rel. standard
deviation srel
0.22 %
Page 94/100 METTLER TOLEDO DL5x and DL7x Titrators
no. 102
Electronics and electroplating applications
Remarks
Method
Method
40011
Version
• The method was developed on the DL40 titrator
Titer Pb(NO3)2
26-01-2001 10:12
Title
Method ID . . . . . . . . . .
Title
. . . . . . . . . .
Date/time . . . . . . . . . .
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
Titration stand . . . . . . .
Temperature sensor . . . . . .
Stir
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
Wait [s] . . . . . . . . .
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
Range . . . . . . . . . . .
Tendency . . . . . . . . .
Termination
at maximum volume [mL] . .
at potential . . . . . . .
at slope . . . . . . . . .
after number EQPs . . . . .
n = . . . . . . . . . .
comb. termination criteria
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
Stop for reevaluation . . .
Condition . . . . . . .
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
Result unit . . . . . . . . .
Result name . . . . . . . . .
Statistics . . . . . . . . . .
Titer
Titrant . . . . . . . . . . .
Concentration . . . . . . . .
Formula
t . . . . . . . . .
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
All results . . . . . . . . .
Raw results . . . . . . . . .
Table of measured values . . .
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
. . . 40011
. . . Titer Pb(NO3)2
. . . 24-01-2001 16:30
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NaF 0.1 M
Fixed volume
5
18.998
1
Stand 1
Manual
. . . 50
. . . 30
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1/2Pb(NO3)2
0.1
DX219
mV
Yes
4.5
30
Incremental
0.1
Equilibrium controlled
0.5
3.0
5.0
45.0
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300
No
No
Positive
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20.0
No
No
Yes
1
No
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Standard
No
No
Yes
neq=0
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R=m/(VEQ*c*C)
C=1/(0.1*z)
5
Titer
Yes
. . . 1/2Pb(NO3)2
. . . 0.1
. . . x
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Printer
No
Yes
No
Yes
No
Yes
Yes
No
No
No
No
No
and has been adapted for the DL5x- and DL7xtitrators.
Sample preparation
1) The standard solution is prepared by dissolving
4.200 g NaF in a 1 L volumetric flask and filling
up to 1 L with deionized water.
The fluoride solution is kept in polyethylene bottles.
2) 5 mL of the standard solution are diluted with 20
mL deionized water, 20 mL isopropanol and 5 mL
0.5 mol/L NaCl.
Reaction
• Fluoride is precipitated by lead according to:
2 F- + Pb2+ = PbF2
• This method can be used for the titration of sulphate
ions.
Chemicals
• Titrant solution :
Dissolve 16.56 g Pb(NO3)2 in a 1 L volumetric
flask and fill up to the mark to obtain the concentration c( 1/2 Pb(NO3)2 ) = 0.1 mol/L
Literature
• DL40 application no. 102.
• C.E. Efstathion, T.P. Hadjhoannon,
Anal. Chim. Acta 109 (1979), p. 319.
Disposal
Special waste.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77.
Electronics and electroplating applications
Authors: Application Laboratory MT-ANA
METTLER TOLEDO DL5x and DL7x Titrators Page 95/100
Literature
1)
"Electrochemistry of semiconductors and Electronics: Processes and Devices", Eds. John
McHardy and Frank Ludwig, Noyes Publications, Park Ridge, New Jersey (USA) 1992 (ISBN
0-8155-1301-1).
2)
Kenneth E. Langford, Janet . Parker,"Analysis of electroplating and related solutions",4th Edition, Robert Draper Ltd, Teddington (UK), 1971 (ISBN 0-8521-8033-0).
3)
Peter Wolfram Wild, "Modern Analysis for Electroplating", Hampton Hill Finishing Publications, 1974.
Peter Wolfram Wild, "Moderne Analyse für die Galvanotechnik", Eugen G. Leuze Verlag, Saulgau (Württemberg), Germany , 1972. (Geman)
4)
Pascal Rast, "Automatisierte Titration zur effizienten Badüberwachung", Seminar SGO (Schweizerische Gesellschaft für Oberflächentechnik), Zürich (CH), 28.10.1987,
Kees Mooibroek, "Analysenverfahren für die Galvanotechnik", DGO Lehrgand (Deutsche Gesellschaft für Oberflächentechnik) , Schwäbisch Gmünd (D), 19.5.1987.
Kees Mooibroek, "Aktuelle Möglichkeiten der Prozessüberwachung bei aussenstromlos arbeitenden Beschichtungsverfahren: Theorie und Praxis", DGO Lehrgang (Deutsche Gesellschaft
für Oberflächentechnik) , Schwäbisch Gmünd (D), 28.3.1990.
5)
METTLER TOLEDO DL21/25 Application Brochure ME-51 724 627 (1995).
METTLER TOLEDO DL70 Appl. Brochure No. 2 "18 Customer Methods"
ME-724492 (1992).
METTLER TOLEDO DL70 Application Brochure No. 4, "Electroplating", ME-724 561
(1994).
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 methods, 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 AG
Analytical
CH-8603 Schwerzenbach, Schweiz
Telefon (01) 806 77 11, Fax (01) 806 73 50
Internet: http://www.mt.com
AT Mettler-Toledo GmbH., A-1100 Wien
Tel. +43-1-604 19 80, Fax +43-1-604 28 80
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Tel. +61-3-9644 5700, Fax +61-3-9645 3935
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Tel. +32-2-334 02 11, Fax +32-2-334 03 34
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Tel. +41-1-944 45 45, Fax +41-1-944 45 10
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Tel. +86-21-6485 0435, Fax +86-21-6485 3351
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Tel. +420-2-25 49 62, Fax +420-2-2424 7583
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Tel. +34-3-223 22 22, Fax +34-3-223 02 71
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Tel. +33-1-3097 1717, Fax +33-1-3097 1616
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Tel. +852-2744 1221, Fax +852-2744 6878
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Tel. +385-1-230 41 47, Fax +385-1-233 63 17
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Tel. +36-1-257 70 30, Fax +36-1-256 21 75
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Tel. +39-2-333 321, Fax +39-2-356 29 73
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Tel. +81-6-949 59 01, Fax +81-6-949 59 45
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Tel. +82-2-518 20 04, Fax +82-2-518 08 13
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Tel. +7- 3272-608 834, Fax +7-3272-608 835
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Tel. +60-3-703 27 73, Fax +60-3-703 17 72
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Tel. +60-3-704 17 73, Fax +60-3-703 17 72
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Tel. +52-5-547 57 00, Fax +52-5-541 22 28
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Tel. +7-095-921 92 11, Fax +7-095-921 63 53
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Tel. +65-7786 779, Fax +65-7786 639
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Tel. +421-7-4342 7496, Fax +421-7-4333 7190
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Tel. +386-61-162 18 01, Fax +386-61-162 17 89
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Tel. +66-2-719 64 80, Fax +66-2-719 64 79
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Tel. +886-2-2579 5955, Fax +886-2-2579 5977
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Tel. +44-116-235 70 70, Fax +44-116-236 63 99
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Tel. +1-614-438 4511, Fax +1-614-438 4900
For all other countries:
Mettler-Toledo GmbH
PO Box, VI-400, CH-8606 Greifensee, Schweiz
Tel. (01) 944 22 11, Fax (01) 944 31 70
Subject to technical changes
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