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METTLER TOLEDO Titrators

Electronics and
electroplating applications
Application brochure 28
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

Page 2/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
M189 Determination of free cyanide in a copper bath ......................................................... 56
M190 Determination of free cyanide in a cyanidic zinc bath .............................................. 58
M191 Back-titration of zinc in a cyanidic zinc bath ............................................................ 60

M175 Titration of gold -Au(III)- in a standard solution ....................................................... 62


M176 Determination of gold by precipitation reaction with hydroquinone ......................... 64
M177 Titer determination of cerium sulfate vs. hydroquinone ............................................ 66
M178 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 ........................................................................................................................................... 96

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 Instruments: METTLER TOLEDO DL70


10 mL Matrix Printer Epson LX800
with serial interface 8148
Substance: Copper (II),
M = 63.546, z = 1 Method: 062

Preparation: 40 mL sulphuric acid 25% Accessories: Titration beakers ME-101974


5 mL Potassium iodide 10 %
5 mL Potassium thiocyanate 10% Indication: DM140-SC at Sensor 2

Titrant: Sodium thiosulphate, Na2 S2O3


c(Na2 S2O3) = 0.1 mol/L

Standard: Potassium iodate, KIO3


(see application M009)

METTLER DL70 Titrator * METTLER - TOLEDO *


Results:
Application Laboratory

062 Chem. Copper Electrolyte measured 20-Jun-1991 13:20


20-Jun-1991 11:28 Titrator Electroplating
SW Version 2.0 User **** KM ****

RESULTS

No Identification Volume Results

1/1 CHEM Cu MD &/2 10.0 mL 1.390 g/L Copper (Cu)


3.490 g/L CuSO4
5.460 g/L CuSO4.5H2O
1/2 CHEM Cu MD &/2 10.0 mL 1.407 g/L Copper (Cu)
3.534 g/L CuSO4
5.529 g/L CuSO4.5H2O
1/3 CHEM Cu MD &/2 10.0 mL 1.398 g/L Copper (Cu)
3.512 g/L CuSO4
5.494 g/L CuSO4.5H2O
1/4 CHEM Cu MD &/2 10.0 mL 1.395 g/L Copper (Cu)
3.504 g/L CuSO4
5.482 g/L CuSO4.5H2O
1/5 CHEM Cu MD &/2 10.0 mL 1.373 g/L Copper (Cu)
3.449 g/L CuSO4
5.396 g/L CuSO4.5H2O

STATISTICS
Number results R1 n = 5
Mean value x = 1.393 g/L Copper (Cu)
Standard deviation s = 0.0126 g/L Copper (Cu)
Rel. standard deviation srel = 0.902 %
Outlier test: no outliers

Page 4/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 062 Chem. Copper Electrolyte
Version 20-Jun-1991 11:28 Bath composition
Title
Method ID . . . . . . . . . . . . . 062
This bath is used for chemical copper deposition on
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . Chem. Copper Electrolyte
. . . . 20-Jun-1991 11:28
printed circuit boards. It consists of sodium hydrox-
Sample ide, formaldehyde, weakly complexed copper, free
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . Stand 1 complexing agent(s), and additives.
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 10.0
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 0.0 Sample preparation
Equivalent number z . . . . . . . . 1
Stir Be careful! If cyanide is present in the sample, the
Speed [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . . . . . . 10 addition of a sulphuric acid solution must be performed
Titration
Titrant . . . . . . . . . . . . . . Na2S2O3 in a ventilated fume hood (formation of HCN!).
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DM140-SC 1) A weak copper complex is decomposed at room
Unit of meas . . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP temperature by the acid medium. A stronger com-
Predispensing 1 . . . . .
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
mL
1.0
plex is decomposed in the same way at elevated
Titrant addition . . . .
∆V [mL] . . . . . . .
.
.
.
.
.
.
.
.
INC
0.1
temperature.
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 2) After decomposition the sample is cooled at room
∆t [s] . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 temperature.
t(max) [s] . . . . . . . . . . 30.0
Threshold
EQP range
. . . . . . .
. . . . . . .
.
.
.
.
.
.
.
.
100.0
Yes
3) Then potassium iodide (KI) and potassium thiocy-
Limit A [mV, pH,...] . . . . . 800.0 anate (KSCN) are added.
Limit B [mV, pH,...] . . . . . 0.0
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes 4) Cu(II) is reduced with excess iodide (I-) and subse-
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard quently precipitated as CuI in the presence of thio-
Calculation
Result name . . . . . . . . . . . . Copper (Cu)
cyanate (SCN-). KSCN is added to avoid adsorp-
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R1=Q*C1/U
C1=63.546/z
tion of I2 on the surface of CuI :
2 Cu2+ + 4 I - → 2 CuI + I2
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . CuSO4
Formula . . . . . . . . . . . . . . R2=Q*C2/U The amount of iodine formed is proportional to the
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C2=159.60/z
g/L
Cu(II) content. Cover the beakers to avoid loss of
Decimal places . . . . . . .
Calculation
. . . . 3 iodine
Result name . . . . . . . . . . . . CuSO4.5H2O
Formula . . . . . . . . . . . . . . R2=Q*C2/U 5) The complete reduction of Cu(II) requires 5 min.
Constant . . . . . . . . . . . . . . C2=249.68/z
Decimal places . . . . . . . . . . . 3
Record
Output unit . . . . . . . .
Result last sample . . . . .
. . . . Printer
. . . . Yes
Titration of iodine
E - V curve . . . . . . . . . . . . Yes
Statistics I2 is titrated at room temperature with Na2S2O3:
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
.
.
.
.
.
.
.
.
R1
Yes 2 S2O32- + I2 → S4O62- + 2 I-
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
• Stir moderately. Vigorous stirring causes loss of I2
Record
Output unit . . . . . . . . . . . . Printer
• Alternative: Photometric indication with DP550
All results . . . . . . . . . . . . Yes Phototrode; indicator: starch
• Titration time: approx. 4 minutes
Literature
E-V curve
1. B. Bressel, Ausserstromloser Kupferelekrolyt,
DGO Deutsche Gesellschaft für Galvano- und
Oberflächentechnik e.V., Horionplatz 6,
Düsseldorf (Germany), 1988
2. Copper bath's manufacturer

Disposal
Copper solutions: special waste

Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators. Author: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 5/100
METTLER TOLEDO

M063 Electroless copper bath: Determination of free complexing agents

Sample: Electroless copper bath Instruments: METTLER TOLEDO DL70


5 mL Matrix Printer Epson LX800
with serial interface 8148
Substance: Complexing agents
Method: 063
Preparation: 60 mL deionised water
Accessories: Titration beakers ME-101974
Titrant: Copper sulphate, CuSO4
c(CuSO4) = 0.01 mol/L Indication: DP550 Phototrode at sensor 2
DIN-Lemo Adapter ME-89600
Standard: EDTA Indicator:
(see application M007) 0.25 g Murexide, 1:500 tritura-
tion with NaCl

Results: METTLER DL70 Titrator Mettler-Toledo AG


Application Laboratory

063 Free Complexing Agents measured 23-Jul-1991 16:24


23-Jul-1991 15:25 Titrator P5
SW Version 2.0 User KM

RESULTS

No Identification Volume Results

1/1 Chem.Cu MD 6/8 5.0 mL 20.408 mmol/L Free Compl.


1/2 Chem.Cu MD 6/8 5.0 mL 20.412 mmol/L Free Compl.
1/3 Chem.Cu MD 6/8 5.0 mL 20.391 mmol/L Free Compl.
1/4 Chem.Cu MD 6/8 5.0 mL 20.414 mmol/L Free Compl.
1/5 Chem.Cu MD 6/8 5.0 mL 20.408 mmol/L Free Compl.

STATISTICS
Number results R1 n = 5
Mean value x = 20.407 mmol/L Free Compl.
Standard deviation s = 0.0089 mmol/L Free Compl.
Rel. standard deviation srel = 0.044 %
Outlier test : sample No. 1/3

Statistics without sample No. 1/3


Number results R1 n = 4
Mean value x = 20.411 mmol/L Free Compl.
Standard deviation s = 0.0029 mmol/L Free Compl.
Rel. standard deviation srel = 0.014 %

Page 6/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 063
Version
Free Complexing Agents
23-Jul-1991 15:25 Bath composition
Title
Method ID . . . . . . . . . . . . . 063
• This bath is used for chemical copper deposition
Title . . . . . . . . . . . . . Free Complexing Agents on printed circuit boards. It consists of sodium hy-
Date/time . . . . . . . . . . . . . 23-Jul-1991 15:25
Sample droxide, formaldehyde, weakly complexed copper,
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . Stand 1 free complexing agent(s), and additives.
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 10.0 • Depending on the use of the bath a single specific
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
********
0.0
complexing agent or a mixture of various complex-
Equivalent number z . . . .
Stir
. . . . 1 ing agents is used. Results are given in mmol/L.
Speed [%] . . . . . . . . . . . . . 40 • The free complexing agents influence the rate of
Time [s] . . . . . . . . . . . . . . 10
Titration copper deposition and the stability of the bath.
Titrant . . . . . . . . . . . . . . CuSO4-(2)
Concentration [mol/L] . . . . . . . 0.01
Sensor . . . . . . . . . . . . . . DP550
Unit of meas . . . . . . . . . . . . mV Sample preparation
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL 1) The copper bath is diluted and then titrated with
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . INC 0.01 M Cu(II) titrant. No pH buffer is added, the
∆V [mL] . . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . EQU sample is alkaline.
∆E [mV] . . . . . . . . . . . 2.0
∆t [s] . . . . . . . . . . . 2.0 2) It is recommended to use a trituration 1:500 murex-
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 ide: NaCl.
Threshold . . . . . . . . . . . 100.0
EQP range . . . . . . . . . . . Yes
Limit A [mV, pH,...] . . . . . 0.0 3) Add the indicator before starting analysis. Keep
Limit B [mV, pH,...] . . . . . 1000.0
Maximum volume [mL] . . . . . . . 40.0 sample free of air bubbles during titration. Air
Termination after n EQPs
n = . . . . . . . . .
.
.
.
.
.
.
.
.
Yes
1
bubbles and undissolved impurities affect with the
Evaluation procedure . .
Calculation
. . . . Standard photometric indication.
Result name . . . . . . . . . . . . Free compl.
Formula . . . . . . . . . . . . . . R1=Q*C1/U
Constant . . . . . . . . . . . . . . C1=1000
Result unit . . . . . . . . . . . . mmol/L Titration
Decimal places . . . . . . . . . . . 3
Record
Output unit . . . . . . . . . . . . Printer
Free complexing agents are titrated with Cu(II)-solu-
Result last sample . . . . . . . . . Yes tion in alkaline solution:
Cu 2+ + Agent → Cu-Agent 2+
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes At the equivalence point (simplified):
Rel. standard deviation srel
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes Cu 2+ + Murexide - → Cu-Murexid + (violet-yellow)
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes • Adjust the DP 550 at 1000 mV in deionised water
before starting titration (100% transmission).
Literature • Due to the steep signal change, an EQP titration
1. B. Bressel, Ausserstromloser Kupferelekrolyt, with fixed increments is used. The low threshold
DGO Deutsche Gesellschaft für Galvano- und value allows for different amounts of indicator.
Oberflächentechnik e.V., Horionplatz 6, • A fixed predispensing shortens the titration time.
Düsseldorf (Germany), 1988. • Titration time: approx. 4 minutes.
2. Copper bath's manufacturer
E-V curve
Disposal
Copper solutions: special waste

Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators.

Author: Kees Mooibroek

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 7/100
METTLER TOLEDO

M064 Electroless copper bath: Sodium hydroxide and formaldehyde


Sample: Electroless copper bath Instruments: METTLER TOLEDO DL70
5 mL Matrix Printer Epson LX800
with serial interface 8148
Substance: Sodium hydroxide, formaldehyde
Method: 064
Preparation: Deionised water, 40 mL
Accessories: Titration beakers ME-101974
Titrant 1: Hydrochloric acid, HCl, 1 additional DV90 burette drive
c(HCl) = 0.1 mol/L 1 additional DV1010 burette
Titrant 2: Sodium sulfite, Na2SO3
c(Na2SO3) = 1 mol/L (pH = 10.5) Indication: DG111-SC at sensor 1

Standard: Tris(hydroxymethyl)aminomethane

064 Hydroxide and Formaldehyde measured 18-Jun-1991 17:18


Results: 18-Jun-1991 11:05 Titrator P5
SW Version 2.0 User KM

RESULTS

No Identification Volume Results

1/1 Chem.Cu MD 4/7 5.0 mL 12.2 pH Dil. sample


14.59 g/L NaOH
-0.59 g/L Correction
8.69 g/L Formaldehyde
-0.19 g/L Correction
1/2 Chem.Cu MD 4/7 5.0 mL 12.3 pH Dil. sample
14.55 g/L NaOH
-0.62 g/L Correction
8.60 g/L Formaldehyde
-0.10 g/L Correction
1/3 Chem.Cu MD 4/7 5.0 mL 12.2 pH Dil. sample
14.62 g/L NaOH
-0.62 g/L Correction
8.60 g/L Formaldehyde
-0.10 g/L Correction
1/4 Chem.Cu MD 4/7 5.0 mL 12.2 pH Dil. sample
14.51 g/L NaOH
-0.51 g/L Correction
8.54 g/L Formaldehyde
-0.04 g/L Correction
1/5 Chem.Cu MD 4/7 5.0 mL 12.2 pH Dil. sample
14.52 g/L NaOH
-0.52 g/L Correction
8.41 g/L Formaldehyde
0.09 g/L Correction

STATISTICS
Number results R1 n = 5
Mean value x = 12.2 pH Dil. sample

STATISTICS
Number results R2 n = 5
Mean value x = 14.56 g/L NaOH
Standard deviation s = 0.047 mmol/L
Rel. standard deviation srel = 0.319 %
Outlier test : no outliers!

STATISTICS
Number results R4 n = 5
Mean value x = 8.58 g/L Formaldehyde
Standard deviation s = 0.109 g/L Formaldehyde
Rel. standard deviation srel = 1.273 %
Outlier test : no outliers!

Page 8/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method
Method 064 Hydroxide and Formaldehyde
Version 18-Jun-1991 11:05 Calculation
Result name . . . . . . . . . . . . Formaldehyde
Title Formula . . . . . . . . . . . . . . R4=Q[2]*C4/U 7
Method ID . . . . . . . . . . . . . 064 Constant . . . . . . . . . . . . . . C4=30.03/1
Title . . . . . . . . . . . . . . . Hydroxide and Result unit . . . . . . . . . . . . g/L
Formaldehyde Decimal places . . . . . . . . . . . 2
Date/time . . . . . . . . . . . . . 18-Jun-1991 11:05 Condition . . . . . . . . . . . . . Yes
Instruction Condition . . . . . . . . . . R2>0
Instruction . . . . . . . . . . . . Analysis to be done Calculation
> . . . . . . . . . . . . . . . . . after correction of Result name . . . . . . . . . . . . Correction
> . . . . . . . . . . . . . . . . . the copper content. Formula . . . . . . . . . . . . . . R5=8.5-(Q[2]*C5/U) 8
Sample Constant . . . . . . . . . . . . . . C5=30.03/1
Number samples . . . . . . . . . . 5 Result unit . . . . . . . . . . . . g/L
Titration stand . . . . . . . . . . Stand 1 Decimal places . . . . . . . . . . . 2
Entry type . . . . . . . . . . . . . Fixed volume U Condition . . . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 5.0 Condition . . . . . . . . . . . R2>0
ID1 . . . . . . . . . . . . . . . . ******** Instruction
Molar mass M . . . . . . . . . . . . 0.0 Instruction . . . . . . . . . . . . Sodium hydroxide
Equivalent number z . . . . . . . . 1 > . . . . . . . . . . . . . . . . . content too high.
Stir > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
Speed [%] . . . . . . . . . . . . . 50 Condition . . . . . . . . . . . . . Yes
Time [s] . . . . . . . . . . . . . . 10 Condition . . . . . . . . . . . R2>16
Measure Instruction
Sensor . . . . . . . . . . . . . . DG111-SC-(2) Instruction . . . . . . . . . . . . Sodium hydroxide
Unit of meas . . . . . . . . . . . . As installed > . . . . . . . . . . . . . . . . . content too low.
∆E [mV] . . . . . . . . . . . . . . 0.5 > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
∆t [s] . . . . . . . . . . . . . . 3.0 Condition . . . . . . . . . . . . . Yes
t(min) mode . . . . . . . . . . . . Fix Condition . . . . . . . . . . . R2<12
t(min) [s] . . . . . . . . . . . 30.0 Instruction
t(max) [s] . . . . . . . . . . . . 300.0 Instruction . . . . . . . . . . . . Formaldehyde content
Calculation > . . . . . . . . . . . . . . . . . too high
Result name . . . . . . . . . . . . Dil. sample > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
Formula . . . . . . . . . . . . . . R1=E Condition . . . . . . . . . . . . . Yes
Constant . . . . . . . . . . . . . . Condition . . . . . . . . . . . R4>10
Result unit . . . . . . . . . . . . pH Instruction
Decimal places . . . . . . . . . . . 1 Instruction . . . . . . . . . . . . Formaldehyde content
1 Titration > . . . . . . . . . . . . . . . . . too low
Titrant . . . . . . . . . . . . . . HCl > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT***
Concentration [mol/L] . . . . . . . 0.1 Condition . . . . . . . . . . . . . Yes
Sensor . . . . . . . . . . . . . . DG111-SC-(2) Condition . . . . . . . . . . . R4<7
Unit of meas . . . . . . . . . . . . As installed Record
Titration mode . . . . . . . . . . . EP Output unit . . . . . . . . . . . . Printer
Predispensing . . . . . . . . . . mL Result last sample . . . . . . . . . Yes
Volume [mL] . . . . . . . . . 1.0 E - V curve . . . . . . . . . . . . Yes
Titrant addition . . . . . . . . Continuous Statistics
Control band [mV, pH,...]. . . 0.3 Ri (i=index) . . . . . . . . . . . . R1
Delay [s] . . . . . . . . . . 10 Statistics
End point mode . . . . . . . . . EPA Ri (i=index) . . . . . . . . . . . . R2
Potential [mV, pH,...] . . . . 10.5 Standard deviation s . . . . . . . . Yes
Tendency . . . . . . . . . . . . Negative Rel. standard deviation srel . . . . Yes
Maximum volume [mL] . . . . . . . 30.0 Outlier test . . . . . . . . . . . . Yes
2 Calculation Statistics
Result name . . . . . . . . . . . . NaOH Ri (i=index) . . . . . . . . . . . . R4
Formula . . . . . . . . . . . . . . R2=Q1*C2/U Standard deviation s . . . . . . . . Yes
Constant . . . . . . . . . . . . . . C2=40/1 Rel. standard deviation srel . . . . Yes
Result unit . . . . . . . . . . . . g/L Outlier test . . . . . . . . . . . . Yes
Decimal places . . . . . . . . . . . 2 Record
3 Calculation Output unit . . . . . . . .
All results . . . . . . . .
. . . . Printer
. . . . Yes
Result name . . . . . . . . . . . . Correction
Formula . . . . . . . . . . . . . . R3=14-(Q1*C3)/U
Constant . . . . . . . . . . . . . . C3=40/1
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 Remarks
Record
Output unit . . . . . . . . . . . . Printer
Result last sample . . . . . . . . . Yes • The electrode DG111-SC is calibrated in the
4 E - V curve . . . . . . . . . . . . Yes
Dispense range of pH 9 to 12 (see application M004).
Titrant . . . . . . . . . . . . . . Na2SO3 (pH 10.5)
Concentration [mol/L] . . . . . . . 1.0
Volume [mL]. . . . . . . . . . . . . 10.0 • Hydrochloric acid is standardized with THAM
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>0 (see application M003).
5 Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60
• The pH value of the sodium sulphite solution
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>0
(Titrant 2) has to be adjusted to the same end-
6 Titration pont value as in the titration (see 6). Otherwise
Titrant . . . . . . . . . . . . . . HCl
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DG111-SC-(2)
complicated blank evaluations are necessary.
Unit of meas . . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EP • Total analysis time: approx. 4 minutes.
Predispensing . . . . . . . . . . mL
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . Continuous • The titrator displays warnings if upper or lower
Control band [mV, pH,...]. . . 0.2
Delay [s] . . . . . . . . . . 10 result limits are exceeded.
End point mode . . . . . . . . . EPA
Potential [mV, pH,...] . . . . 10.5
Tendency . . . . . . . . . . . . Negative
Maximum volume [mL] . . . . . . . 30.0
Condition . . . . . . . . . . . . Yes

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 9/100
Comments to method 064
1. EPA Titration:
Continuous endpoint titration to pH 10.5, i.e. the pH value of endpoint as indicated in the litera-
ture of the manufacturer. No overtitration. This titration allows the determination of the NaOH-
content.
2. Calculation R2:
NaOH-content in g/L.
3. Calculation R3:
Calculation of the bath correction in g NaOH/L This value is the difference between the nominal
value 14 and the actual result. The nominal value is indicated by the manufacturer.
4. Dispense:
10 mL sodium sulphite solution c(Na2SO3) = 1.0 mol/L are dispensed. The pH value of this
reagent must first be adjusted according to the pH endpoint of the subsequent EPA titration (see
6) , in this case pH 10.5.
5. Stir:
During stirring time the following reaction takes place:

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 conce-
tration of formaldehyde is determined.
7. Calculation R4:
Calculation of the formaldehyde content in g/L
8. Calculation R5:
Calculation of the bath correction in g formaldehyde/L . This value is the difference between the
nominal value 8.5 and the actual result. The nominal value is indicated by the manufacturer.

Bath composition
• The electroless alkaline copper bath is used for the deposition of relatively thick layers of copper
on printed circuit boards. The procedure is based on the chemical reduction of (weakly) complexed
copper (II) ions at activated catalytic surfaces.
• This type of bath usually contains copper, complexing agent or mixture of complexing agents,
alkali (e.g. NaOH), formaldehyde as a reducing agent, and additives.
• The periodic bath control by titration is necessary for optimal applicaition of the bath., The content
of copper (II) ions (see application M062), of free complexing agents (M063), of hydroxide and
formaldehyde as well as the pH value (this application) are determined. Concentrations values
outside the limits cause failures.

Page 10/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
E-V curve: NaOH content E-V curve: Formaldehyde content

Literature
1. B. Bressel, Ausserstromloser Kupferelekrolyt, DGO Deutsche Gesellschaft für Galvano- und
Oberflächentechnik e.V., Horionplatz 6, Düsseldorf (Germany), 1988
2. Copper bath's manufacturer

Disposal
Copper solutions: special waste

Other titrators
DL77 titrator.

Author: Kees Mooibroek


Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 11/100
METTLER TOLEDO

M065 Electroless nickel bath: Determination of sodium hypophosphite

Sample: Electroless nickel bath Standard: For Na2S2O3: Potassium iodate


3 mL
Instruments: METTLER TOLEDO DL70
Substance: Sodium hypophosphite monohydrate, Matrix Printer Epson LX800
NaH2PO2 • H2O, M = 105.99 with serial interface 8148

Preparation: - H2SO4 (20%), 50 mL Method: 065a, 065b


- I2 , c(1/2 I2) = 0.1 mol/L, 20 mL -
Oxidation reaction time: 60 min Accessories: Titration beakers ME-23828
(in the dark) (brown glass beaker)
1 additional DV90 burette drive
Titrant 1: Iodine, I2 , c(1/2 I2) = 0.1 mol/L, 1 additional DV1010 burette

Titrant 2: Na2S2O3 , c(Na2S2O3)= 0.1 mol/L Indication: DM140-SC at sensor 2

Results: 065a Hypophosphite in Chem.Ni measured 18-Nov-1991 15:28


18-Nov-1991 14:51 Titrator P 5
SW Version 2.0 User KM

RESULTS

No Identification Volume Results

1/1 Chem.Ni 13/40 3.0 mL 29.06 g/L NaH2PO2


35.01 g/L NaH2PO2•H2O
-9.01 g/L Correction
1/2 Chem.Ni 13/45 3.0 mL 28.93 g/L NaH2PO2
34.85 g/L NaH2PO2•H2O
-8.85 g/L Correction
1/3 Chem.Ni 13.50 3.0 mL 29.10 g/L NaH2PO2
35.06 g/L NaH2PO2•H2O
-9.06 g/L Correction
1/4 Chem.Ni 13.55 3.0 mL 29.26 g/L NaH2PO2
35.25 g/L NaH2PO2•H2O
-9.25 g/L Correction
1/5 Chem.Ni 13.60 3.0 mL 29.00 g/L NaH2PO2
34.94 g/L NaH2PO2•H2O
-8.94 g/L Correction

STATISTICS
Number results R1 n = 5
Mean value x = 29.07 g/L NaH2PO2

STATISTICS
Number results R2 n = 5
Mean value x = 35.02 g/L NaH2PO2•H2O
Standard deviation s = 0.150 g/L NaH2PO2•H2O
Rel. standard deviation srel = 0.428 %
Outlier test: no outliers!

STATISTICS
Number results R3 n = 5
Mean value x = -9.02 g/L Correction

Page 12/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 065a / Content determination Remarks
Method 065a Hypophosphite in Chem.Ni
Version 18-Nov-1991 14:51

Title Bath composition


Method ID . . . . . . . . . . . . . 065a
Title . . . . . . . . . . . . . Hypophosphite in Chem.Ni
Date/time . . . . . . . . . . . . . 18-Nov-1991 14:51 • This bath consists of nickel salts, sodium hy-
Sample
Number samples . . . . . . . . . . 5 pophosphite, buffering compounds, stabilisers,
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U accelerators, wetting and complexing agents.
Volume [mL] . . . . . . . . . . . 3.0
ID1 . . . . . . . . . . . . . . . . ******** Decomposition products are formed during use
Molar mass M . . . . . . . . . . . . 89.978
Equivalent number z . . . . . . . . 2 of the bath.
Stir
Speed [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . . . . . . 5
Titration Sample preparation (Method 065a)
Titrant . . . . . . . . . . . . . . Na2S2O3
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DM140-SC 1) 2 mL sample are diluted with 50 mL sulphuric
Unit of meas . . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP acid solution 20%.
Predispensing 1 . . . . . . . . . mL
Volume [mL] . . . . .
Titrant addition . . . .
.
.
.
.
.
.
.
.
0.0
DYN 2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
∆E(set)[mV] . . . . .
Limits ∆V . . . . . .
.
.
.
.
.
.
.
.
8.0
Relative dispensed with a burette ("Titrant 1") to the
∆V(min) [%dosVol] .
∆V(max) [%buVol]. .
.
.
.
.
.
.
.
.
0.5
2.5 acidified sample using the auxiliary function
Measure mode . . . . . .
∆E [mV] . . . . . . .
.
.
.
.
.
.
.
.
EQU
1.0 "Dosing" of the titrator. After dispensing
∆t [s] . . . . . . .
t(min) [s] . . . . . .
.
.
.
.
.
.
.
.
3.0
3.0 cover the titration beaker by e.g. a watch glass.
t(max) [s] . . . . . . . . . . 30.0
Threshold
EQP range
. . . . . . .
. . . . . . .
.
.
.
.
.
.
.
.
150.0
Yes
3) This oxidation is carried out at room tempera-
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
.
.
.
.
.
.
.
.
1000.0
-1000.0
ture in the dark. Cover the beaker to prevent
Maximum volume [mL] . . .
Termination after n EQPs
.
.
.
.
.
.
.
.
30.0
Yes
loss of iodine:
n = . . . . . . . . . . . . . 1
Evaluation procedure . .
Calculation
. . . . Standard I2 + H2PO2- + H2O = 2I- + HPO32- +3H+
Result name . . . . . . . . . . . . NaH2PO2
Formula . . . . . . . . . . . . . . R1=(H3-Q1)*C1/U The reaction requires 60 minutes to complete.
Constant . . . . . . . . . . . . . . C1=M/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 4) Oxidising agents stronger than iodine may
Calculation
Result name . . . . . . . . . . . . NaH2PO2•H2O cause side reactions with organic bath compo-
Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U
Constant . . . . . . . . . . . . . . C2=105.99/z nents or decomposition products.
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Calculation 5) The amount of substance of the dispensed io-
Result name . . . . . . . . . . . . Correction
Formula . . . . . . . . . . . . . . R3=26-((H3-Q1)*C3/U) dine solution is determined with method 065b
Constant . . . . . . . . . . . . . . C3=105.99/1
Result unit . . . . . . . . . . . . g/L (see next page).
Decimal places . . . . . . . . . . . 2
Instruction
Instruction . . . . . . . . . . . . Sodium hypophosphite
> . . . . . . . . . . . . . . . . . monohydrate content Content determination (Method 065a)
> . . . . . . . . . . . . . . . . . too high.Pls.correct
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . R2>29 1) The content of sodium hypophosphite is deter-
Instruction
Instruction . . . . . . . . . . . . Sodium hypophosphite mined by an iodometric backtitration. Excess
> . . . . . . . . . . . . . . . . . monohydrate content
> . . . . . . . . . . . . . . . . . too low.Pls.correct iodine is dispensed (sample preparation) in
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . R2<23 order to oxidise hypophosphite in the acidic
Record
Output unit . . . . . . . . . . . . Printer solution. The remaining excess iodine is ti-
Result last sample . . . . . . . . . Yes
Table of measured values . . . . . . Yes trated with sodium thiosulphate:
E - V curve . . . . . . . . . . . . Yes

I2 + 2 S2O32- → 2I- + S4O62-


Statistics
Ri (i=index) . . . . . . . . . . . . R1
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes 2) Sodium thiosulphate is standardized with po-
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes tassium iodate (see application M009).
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
.
.
.
.
.
.
.
.
R4
Yes
3) The titrator displays warnings if upper or lower
Rel. standard deviation srel
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes
result limits are exceeded.
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . 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 measured 18-Nov-1991 15:19


18-Nov-1991 14:51 Titrator P 5
SW Version 2.0 User KM

RESULTS

No Identification Volume Results

1/1 Chem.Ni 13.55 3.0 mL 29.26 g/L NaH2PO2


35.25 g/L NaH2PO2•H2O
-9.25 g/L Correction

SAMPLE
No. 1/4
Titration stand Stand 1
Identification Chem.Ni 13.55
Volume U = 3.0 mL
Correction factor f = 1.0

MEASURED VALUES
Titrant Na2S2O3 0.1 mol/L t = 0.99896
Drive Drive 2 20 mL
Sensor DM140-SC

Volume Increment Signal Change 1st deriv. Time


mL mL mV mV mV/mL min:s

E1 0.0000 284.0 0:03


0.0040 0.0040 283.8 -0.2 -52.5 0:07
0.0080 0.0040 283.4 -0.4 -94.5 0:12
E2 0.0120 0.0040 283.3 -0.2 -38.5 0:15
0.0220 0.0100 283.2 -0.1 -5.6 0:19
0.0480 0.0260 281.8 -1.4 -53.8 0:26
0.1120 0.0640 264.0 -17.9 -278.9 0:36
0.1280 0.0160 264.0 0.0 1.8 0:40
0.1420 0.0140 256.0 -8.0 -568.0 0:49
0.1500 0.0080 242.7 -13.3 -1664.2 0:56
0.1540 0.0040 221.9 -20.8 -5211.4 1:17
EQP1 0.1580 0.0040 191.0 -30.9 -7720.9 1:48
0.1620 0.0040 179.6 -11.4 -2838.4 2:08
0.1660 0.0040 178.7 -1.0 -241.5 2:11

Method 065a / Content determination

Page 14/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 065b / Iodine solution Remarks
Method 065b Aux. value for M065/M067
Version 19-Nov-1991 14:12
Sample preparation Method 065b
Title
Method ID . . . . . . . . .
Title . . . . . . . . .
. . . . 065b
. . . . Aux. value for M065/M067
1) 50 mL sulphuric acid solution 20% are given
Date/time . . . . . . . . .
Sample
. . . . 19-Nov-1991 14:12 into a titration beaker.
Number samples . . . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1 2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 0.0 dispensed automatically by the titrator using
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 0.0 the function "Dispense" in method 065b.
Equivalent number z . . . . . . . . 1
Stir
Speed [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . .
Dispense
. . . . 5
Titration
Titrant . . . . . . . . . . . . . . 1/2 I2
Concentration [mol/L] . . . . . . . 0.1
Volume [mL] . . . . . . . . . . . . 20.0 1) Iodine is titrated with sodium thiosulphate:
Stir
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 40
. . . . 20
I2 + 2 S2O32- → 2 I- + S4O62-
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
Na2S2O3
0.1
2) Sodium thiosulphate is standardized with po-
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
.
.
.
.
.
.
.
.
DM140-SC
mV
tassium iodate (see application M009).
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL 3) The mean value of a series of three sample is
Volume [mL] . . . . . . . . . 15.0
Titrant addition . . . . . . . . DYN automatically stored as auxiliary value H3 and
∆E(set)[mV] . . . . . . . . . 4.0
Limits ∆V . . . . . . . . . . Relative can therefore by applied by method 065a for
∆V(min) [%dosVol] . . . . . 0.1
∆V(max) [%buVol]. . . . . . 1.5 the determination of nickel.
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 3.0 4) The storage of the mean value only occurs if it
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 is comprised between the limits 1.5 and 2.5
Threshold . . . . . . . . . . . 150.0
EQP range . . . . . . . . . . . Yes mmol which assure an adequate cocnentration.
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . -1000.0
Maximum volume [mL] . . . . . . . 30.0 5) The shelf life of the iodine solution is limited.
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 We recommend to perfom method 065b before
Evaluation procedure . . . . . . Standard
Calculation each nickel content determination.
Result name . . . . . . . . . . . . Consumption
Formula . . . . . . . . . . . . . . R1=Q1
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mmol
Decimal places . . . . . . . . . . . 4
Record
Output unit . . . . . . . . . . . . Printer
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Auxiliary value
ID text . . . . . . . . . . . . . . Aux.M065/M067
Formula . . . . . . . . . . . . . . H3=x[1]
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . 1.5<x<2.5
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes

Method 065b / Iodine concentration

Disposal
Nickel solutions: special waste

Other titrator
DL77 titrator.

Author: Kees Mooibroek

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 15/100
METTLER TOLEDO

M066 Electroless nickel bath: Determination of nickel

Sample: Electroless nickel bath Instruments: METTLER TOLEDO DL70


5 mL Matrix Printer Epson LX800
with serial interface 8148
Substance: Nickel, M = 58.69 g/mol
Method: 066
Preparation: - Deionised water, 50 mL
- Buffer pH 10, 10 mL Accessories: Titration beakers ME-101974
- 0.25 g Murexide trituration
with NaCl (1:500). Indication: - DP550 Phototrode at sensor 2
- Indicator: Murexide trituration
Titrant: EDTA, c(EDTA) = 0.1 mol/L

Standard: Zinc sulfate, c(ZnSO4) = 0.1 mol/L


(See METTLER method M007)

Results: 066 Ni in Chem. Ni-Electrolyte measured 13-Sep-1991 14:23


13-Sep-1991 13:39 Titrator P5
SW Version 2.0 User KM

RESULTS

No Identification Volume Results

1/1 CHEM.Ni LR-200 5.0 mL 5.75 g/L Ni Content


1/2 CHEM.Ni LR-200 5.0 mL 5.74 g/L Ni Content
1/3 CHEM.Ni LR-200 5.0 mL 5.77 g/L Ni Content
1/4 CHEM.Ni LR-200 5.0 mL 5.75 g/L Ni Content
1/5 CHEM.Ni LR-200 5.0 mL 5.74 g/L Ni Content
1/6 CHEM.Ni LR-200 5.0 mL 5.73 g/L Ni Content

STATISTICS
Number results R1 n = 6
Mean value x = 5.74 g/L Ni Content
Standard deviation s = 0.012 g/L Ni Content
Rel. standard deviation srel = 0.211 %
Outlier test: no outliers!

Page 16/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 066 Remarks
Method 066 Ni in Chem. Ni-Electrolyte
Version 13-Sep-1991 13:39 • The buffer pH 10 is prepared by addition of
Title 570 mL conc. NH3 and 70 g NH4Cl in a 1 L flask.
Method ID . . . . . . . . . . . . . 066
Title . . . . . . . . . . . . . Ni in Chem. Ni-Electrolyte
Deionised water is added to 1 L.
Date/time . . . . . . . . . . . . . 13-Sep-1991 13:39
Instruktion • The shape of the titration curve is somewhat af-
Instruction . . . . . . . . . . . . 10mL NH3-Buffer, pH 10
> . . . . . . . . . . . . . . . . . + ca. 200 mg 1 : 500 fected by the concentration of the indicator. The
> . . . . . . . . . . . . .
Sample
. . . . Murexide trituration
results, however, do not differ significantly (tested
Number samples . . . . . .
Titration stand . . . . . .
.
.
.
.
.
.
.
.
6
Stand 1
range: 25-500 mg 1:500 murexide : NaCl tritura-
Entry type . . . . . . . . . . . . . Fixed volume U tion pe sample).
Volume [mL] . . . . . . . . . . . 5.0
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 58.69 • The results are given in g/L using the molar mass
Equivalent number z . . . . . . . . 1
Stir
M.
Speed [%] . . . . . . . . . . . . . 60
Time [s] . . . . . . . . . . . . . . 10 M(Ni) = 58.69 g/mol
Titration
Titrant . . . . . . . . . . . . . . EDTA
Concentration [mol/L] . . . . . . . 0.1 M(NiCl2) = 129.6 g/mol
Sensor . . . . . . . . . . . . . . DP550
Unit of meas . . . . . . . .
Titration mode . . . . . . .
.
.
.
.
.
.
.
.
As installed
EQP
M(NiCl2•6H2O) = 237.7 g/mol.
Predispensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 1.0 • Nickel ions forms a yellow complex with murex-
Titrant addition . . . . . . . . DYN
∆E(set)[mV] . . . . . . . . . 8.0 ide in alkaline solution:
Limits ∆V . . . . . . . . . . Absolute
∆V(min) . . . . . .
∆V(max) . . . . . .
.
.
.
.
.
.
.
.
0.05
0.2
Ni 2+ + Murexide - = Ni-Murexid+
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 2.0 By adding EDTA, Ni forms a more stable complex
∆t [s] . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 2.0 with EDTA:
t(max) [s] . . . . . . . . . . 15.0
Threshold
EQP range
. . . . . . .
. . . . . . .
.
.
.
.
.
.
.
.
10.0
Yes
Ni-Murexid+ + EDTA 4- = Ni-EDTA2-+ Murexide-
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . 0.0 At the equivalence point, all Ni ions have been
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes complexed by EDTA and murexide is free in the
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard alkaline solution. There is a colour change from
Calculation
Result name . . . . . . . . . . . . Ni Content
yellow to blue-violet.
Formula . . . . . . . . . . . . . . R1=Q*C1/U
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C1=M/z
g/L
• Nickel content of different baths:
Decimal places . . . . . . . . . . . 2
Record Bath n Content / g/L srel / %
Output unit . . . . . . . . . . . . Printer
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics LR-6/A 5 5.65 0.254
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
.
.
.
.
.
.
.
.
R1
Yes
LR-37K 6 5.67 0.253
Rel. standard deviation srel . . . . Yes LR-200 6 5.74 0.211
Outlier test . . . . . . . . . . . . Yes
Record ALT/IC 5 5.38 0.128
Output unit . . . . . . . .
All results . . . . . . . .
. . . . Printer
. . . . Yes
NM/a-1 6 5.36 0.206
IG/3-6 6 6.41 0.219

Literature 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: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 17/100
METTLER TOLEDO

M067 Electroless nickel bath: Determination of sodium orthophosphite

Sample: Electroless nickel bath Standard: For Na2S2O3 : Potassium iodate


0.5 mL
Instruments: METTLER TOLEDO DL70
Substance: Sodium orthophosphite, Na2HPO3 Matrix Printer Epson LX800
M = 125.96 g/mol, z = 2 with serial interface 8148

Preparation: - 20 mL 5% NaHCO3 solution Method: 067


- 20 mL Iodine solution
c(1/2 I2) = 0.1 mol/L Accessories: Titration beakers ME-23828
- Oxidation reaction time in the (brown glasses)
dark: 30 min. Two additional drives DV90
Two additional burettes DV1020
Titrant 1: Iodine, c(1/2 I2) = 0.1 mol/L
Titrant 2: Acetic acic, c(CH3COOH) = 2 mol/L Indication: DM140-SC at Sensor 2
Titrant 3: Sodium thiosulphate,
c(Na2S2O3) = 0.1 mol/L
Results: 067 Orthophosphite in Chem. Ni measured 21-Nov-1991 17:23
21-Nov-1991 12:44 Titrator P 5
SW Version 2.0 User KM

RESULTS

No Identification Volume Results

1/1 Chem.Ni 28/10B 0.5 mL 190.03 g/L Na2HPO3


156.87 g/L NaH2PO3
123.71 g/L H3PO3
1/2 Chem.Ni 28/10B 0.5 mL 189.67 g/L Na2HPO3
156.57 g/L NaH2PO3
123.47 g/L H3PO3
1/3 Chem.Ni 28/10B 0.5 mL 189.82 g/L Na2HPO3
156.69 g/L NaH2PO3
123.57 g/L H3PO3
1/4 Chem.Ni 28/10B 0.5 mL 190.05 g/L Na2HPO3
156.88 g/L NaH2PO3
123.71 g/L H3PO3
1/5 Chem.Ni 28/10B 0.5 mL 189.98 g/L Na2HPO3
156.83 g/L NaH2PO3
123.67 g/L H3PO3
1/6 Chem.Ni 28/10B 0.5 mL 189.87 g/L Na2HPO3
156.73 g/L NaH2PO3
123.60 g/L H3PO3
1/7 Chem.Ni 28/10B 0.5 mL 189.48 g/L Na2HPO3
156.41 g/L NaH2PO3
123.35 g/L H3PO3
1/8 Chem.Ni 28/10B 0.5 mL 189.95 g/L Na2HPO3
156.80 g/L NaH2PO3
123.65 g/L H3PO3

STATISTICS
Number results R1 n = 8
Mean value x = 189.86 g/L Na2HPO3
Standard deviation s = 0.196 g/L Na2HPO3
Rel. standard deviation srel = 0.103 %
Outlier test: no outliers!

STATISTICS
Number results R2 n = 8
Mean value x = 156.72 g/L NaH2PO3

STATISTICS
Number results R3 n = 8
Mean value x = 123.59 g/L NaH2PO3

Page 18/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method 067 Remarks
Method 067 Orthophosphite in Chem.Ni
Version 21-Nov-1991 12:44 Electroless nickel bath
Title
Method ID . . . . . . . . . . . . . 067 • Orthophosphite affects the behaviour of the bath.
Title . . . . . . . . . . . . . Orthophosphite in Chem.Ni
Date/time . . . . . . . . . . . . . 21-Nov-1991 12:44
The bath must be replaced as soon as a specific
Sample
Number samples . . . . . . . . . . 8
concentration is reached.
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.5
********
Sample preparation (Method 067)
Molar mass M . . . . . . . . . . . . 0.0
Equivalent number z . . . . . . . . 2 1) Add 20 mL 5% NaHCO3 to the sample.
Dispense
Titrant . . . . . . . . . . . . . . Acetic acid
Concentration [mol/L] . . . . . . . 2 2) 20 mL iodine c(1/2 I2) = 0.1 mol/L are dispensed
Volume [mL] . . . . . . . . . . . . 20.0
Stir using the auxiliary function "Dosing" of the titra-
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 40
. . . . 20
tor. Cover the beaker to prevent loss of iodine.
Titration
Titrant . . . . . . . . . . . . . . Na2S2O3 3) This oxidation is carried out at room temperature in
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . DM140-SC the dark during 30 minutes :
Unit of meas . . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL I2 + HPO32- + 3 OH - = 2I- + PO43- + 2 H2O
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . DYN
∆E(set)[mV] . . . . . . . . . 8.0
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
.
.
.
.
.
.
.
.
Relative
0.5
Procedure
∆V(max) [%buVol]. . . . . . 2.5
Measure mode . . . . . . . . . . EQU • The orthophosphite concentration is determined by
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 3.0 an iodometric back titration.
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 • The iodine concentration is determined by a simi-
Threshold . . . . . . . . . . . 150.0
EQP range . . . . . . . . . . . Yes lar method as 067. The result (mmol) is stored as
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . -1000.0 auxiliary value H3 and used for the back-titration.
Maximum volume [mL] . . . . . . . 30.0
Termination after n EQPs . . . . Yes • The sample is acidified with 20 mL 2 mol/L acetic
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard acid immediately before titration.
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
Na2HPO3
R1=(H3-Q1)*C1/U
• The iodine excess is then titrated with method 067.
Constant . . . . . . . . . . . . . . C1=125.9589/z
Result unit . . . . . . . . . . . . g/L • If the orthophosphite concentration exceeds the lim-
Decimal places . . . . . . . . . . . 2
Calculation it of 200 g/L an instruction is displayed.
Result name . . . . . . . . . . . . NaH2PO3
Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U
Constant . . . . . . . . . . . . . . C2=103.9768/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 Nickel content of different baths
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
H3PO3
R3=(H3-Q1)*C3/U
Bath n Content/ g/L srel/%
Constant . . . . . . . . . . . . . . C3=81.9947/z
Result unit . . . . . . . . . . . . g/L 28/10 A 3 189.00 0.158
Decimal places . . . . . . . . . . . 2
Instruction 28/10 B 8 189.66 0.103
Instruction . . . . . . . . . . . . CHECK CONCENTRATION
> . . . . . . . . . . . . . . . . . OF PHOSPHITE G601 6 184.26 0.121
> . . . . . . . . . . . . . . . . .
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>200 Disposal
Record
Output unit . . . . . . . . . . . . Printer Nickel solutions: special waste
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
E-V curve
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Standard deviation s . . . . . . . . Yes
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes

Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77. Author: Kees Mooibroek

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 19/100
METTLER TOLEDO

M151 Determination of acetic, phosphoric and nitric acid in a mixture

Sample: Acid mixture Instruments: METTLER TOLEDO DL58


1 mL METTLER TOLEDO ST20A
Printer EPSON SC600
Substance: Acetic acid HAc
Phosphoric acid H3PO4 Method: Mix
Nitric acid, HNO3
Accessories: Titration beakers ME-101974
Preparation: 50 mL deion. water Peristaltic pump ME-65241

Titrant: Sodium hydroxide, NaOH Indication: DG111-SC


c(NaOH) = 0.1 mol/L

Standard: Potassium hydrogen phtalate

Results: METTLER TOLEDO DL58 Titrator V2.0 MTCS ANA MS


Application Lab

Method Mix HAc+HNO3+H3PO4 16-Mar-1999 17:18


Measured 17-Mar-1999 16:20
User Li Pei

ALL RESULTS

No. ID Sample size and results

1 Mix. Acid 1.0 mL


R1 = 0.9689 mol/L HAc content
R2 = 0.9894 mol/L H3PO4 content
R3 = 0.4461 mol/L HNO3 content
2 Mix. Acid 1.0 mL
R1 = 0.9574 mol/L HAc content
R2 = 0.9855 mol/L H3PO4 content
R3 = 0.4439 mol/L HNO3 content
3 Mix. Acid 1.0 mL
R1 = 0.9530 mol/L HAc content
R2 = 0.9835 mol/L H3PO4 content
R3 = 0.4387 mol/L HNO3 content

STATISTICS
Number results R1 n = 3
Mean value x = 0.9598 mol/L HAc content
Standard deviation s = 0.00824 mol/L HAc content
Rel. standard deviation srel = 0.859 %

STATISTICS
Number results R2 n = 3
Mean value x = 0.9862 mol/L H3PO4 content
Standard deviation s = 0.00300 mol/L H3PO4 content
Rel. standard deviation srel = 0.304 %

STATISTICS
Number results R3 n = 3
Mean value x = 0.4429 mol/L HNO3 content
Standard deviation s = 0.00384 mol/L HNO3 content
Rel. standard deviation srel = 0.867 %

Page 20/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method Mix HAc+HNO3+H3PO4
Version 16-Mar-1999 17:18 • This titration procedure includes four steps:
Title 1. HNO3 = H+ + NO3-
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . Mix
. . . HAc+HNO3+H3PO4 2. H3PO4 = H+ + H2PO4-
Date/time . . . . . . . . . .
Sample
. . . 21-Nov-1991 12:44
3. HAc = H+ + Ac-
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Mix. Acid
Fixed volume 4. H2PO4 -
= H+ + HPO42-
Volume [mL] . . . . . . . . . . . 1.0
Molar mass M . . . . . . . . . . . . 100
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . . . . . ST20A Due to the little difference between the pKa-
Pump . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O value of HNO3 (pKa=approx. -1.3) and H3PO4
Volume [mL] . . . . . . . . . 50.0
Stir . . . . . . . . . . . . . No (pKa1=2.12), the first two steps can not be dis-
Pump . . . . . . . . . . . . . . No
Rinse . . . . . . . . . . . . . . Yes tinguished. Therefore only three potential
Solvent . . . . . . . . . . . H2O
Volume [mL] . . . . . . . . . 10.0 jumps can be seen on the titration curve.
Conditioning . . . . . . . . . . No
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50 • A sample changer ST20A is used in this meth-
Time [s] . . . . . . . . . . . . . . 10
EQP titration od for a fully automatic procedure. The meth-
Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH od can be easily modified for manual opera-
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DG111 tion: enter "Stand 1" as titration stand in the
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . to volume function SAMPLE.
Volume [mL] . . . . . . . . . . . 2.5
Wait time [s] . . . . . . . . . . 0
Titrant addition . . . . . . . . . . Dynamic
∆E(set)[mV]
∆V(min)[mL]
. . . . . . .
. . . . . . .
.
.
.
.
.
.
8.0
0.02
Disposal
∆V(max)[mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 1.0 Neutralization with hydrochloric acid.
∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . . 2.0
t(max) [s] . . . . . . . . . . . 10.0
Recognition
Threshold . . . . . . . . . . . . 17.0
Other titrators
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No DL50 Graphix, DL53/DL55, DL70ES, DL77.
Tendency . . . . . . . . . . . . None
Termination
at maximum volume [mL] . . . . . 40.0
at potential . . . . . . . . . . No
at slope . . . . . . . . .
after number EQPs . . . . .
.
.
.
.
.
.
No
Yes
E-V curve
n = . . . . . . . . . . . . . 3
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . No
Calculation
Formula . . . . . . . . . . . . . . R1=Q2*C1/m
Constant . . . . . . . . . . . . . . C1=1/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mol/L
Result name . . . . . . . . . . . . HAc content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=Q3*C2/m
Constant . . . . . . . . . . . . . . C2=1/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mol/L
Result name . . . . . . . . . . . . H3PO4 content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=(Q1-Q3)*C3/m
Constant . . . . . . . . . . . . . . C3=1/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mol/L
Result name . . . . . . . . . . . . HNO3 content
Statistics . . . . . . . . . . . . . Yes
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . No
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . No
∆E/∆V - V curve . . . . . . . . . . No
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Author: Li Pei
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 21/100
METTLER TOLEDO

M152 Nitric, acetic and phosphoric acid mixture: large excess of phosphoric acid

Sample: Acid cleaner Instruments: METTLER TOLEDO DL58


0.5 g METTLER TOLEDO ST20A
Printer EPSON SC600
Substance: Nitric acid, HNO3 ; Acetic acid
HAc; Phosphoric acid H3PO4 Method: 2.2
HNO3 : HAc : H3PO4 = approx. 1 : 4 : 23
Accessories: Titration beakers ME-101974
Preparation: 50 mL deion. water Peristaltic pump ME-65241
(dispensed by pump)
Indication: DG111-SC
Titrant: Sodium hydroxide, NaOH
c(NaOH) = 1 mol/L

Standard: Potassium hydrogen phtalate


Results: Method 2.2 EQP Titration 07/17/2000 13:59
Measured 07/17/2000 14:48
User YY

ALL RESULTS

No. ID Sample size and results

1 0.5102 g
R1 = 3.0723 % HNO3 content
R2 = 12.2359 % HAc content
R3 = 70.9786 % H3PO4 content
2 0.5199 g
R1 = 3.0858 % HNO3 content
R2 = 12.0854 % HAc content
R3 = 70.8494 % H3PO4 content
3 0.518 g
R1 = 2.9778 % HNO3 content
R2 = 11.9648 % HAc content
R3 = 70.9050 % H3PO4 content
4 0.5373 g
R1 = 3.1480 % HNO3 content
R2 = 11.8686 % HAc content
R3 = 70.7380 % H3PO4 content
5 0.5176 g
R1 = 3.0152 % HNO3 content
R2 = 11.7205 % HAc content
R3 = 70.7452 % H3PO4 content
6 0.5078 g
R1 = 3.0452 % HNO3 content
R2 = 11.6033 % HAc content
R3 = 70.6551 % H3PO4 content

STATISTICS
Number results R1 n = 6
Mean value x = 3.0574 % HNO3 content
Standard deviation s = 0.05917 % HNO3 content
Rel. standard deviation srel = 1.935 %

STATISTICS
Number results R2 n = 6
Mean value x = 11.9131 % HAc content
Standard deviation s = 0.23308 % HAc content
Rel. standard deviation srel = 1.957 %

STATISTICS
Number results R3 n = 6
Mean value x = 70.8119 % H3PO4 content
Standard deviation s = 0.12031 % H3PO4 content
Rel. standard deviation srel = 0.170 %

Page 22/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 2.2 EQP Titration
Version 07/17/2000 13:59
Title • This titration procedure includes four steps:
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . 2.2
. . . EQP Titration 1. HNO3 = H+ + NO3-
Date/time . . . . . . . . . .
Sample
. . . 07/17/2000 13:59
2. H3PO4 = H+ + H2PO4-
=
Sample ID . . . . . . . . . . . . .
Entry type . . . . . . . . . . . . . Weight 3. HAc H+ + Ac-
=
Lower limit [g] . . . . . . . . . 0.4
Upper limit [g] . . . . . . . . . 0.6 4. H2PO4- H+ + HPO42-
Molar mass M . . . . . . . . . . . . 98
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . ST20A
Pump . . . . . . . . . . . . . . Yes Due to the little difference between the pKa-value
Solvent . . . . . . . . . . . H2O
Volume [mL] . . . . . . . . . 50.0 of HNO3 and H3PO4 ,the first two steps can not be
Stir . . . . . . . . . . . . . No
Pump . . . . . . . . . . . . . . No distinguished. Therefore only three potential jumps
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O can be seen on the titration curve.
Volume [mL] . . . . . . . . . 20.0
Conditioning . . . . . . . . . . Yes
Time [s] . . . . . . . .
Interval . . . . . . . .
.
.
.
.
.
.
20
1 • The two potential jumps are evaluated at potential
Rinse . . . . . . . . . . . . No
Temperature sensor . . . . . . . . . Manual
values of pH 3.75 and 5.5 (see evaluation). These
Stir
Speed [%] . . . . . . . . . . . . . 50
values are determined by a trial titration. From the
Time [s] . . . . . . . . . . .
EQP titration
. . . 10 table of measured values the pH values correspond-
Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH
ing to the potential jumps can be easily determined.
Concentration [mol/L] . . . . . . 1.0 The values are then used for sample analysis.
Sensor . . . . . . . . . . . . . DG111
Unit of meas. . . . . . . . . . . pH Note that these values depend on the concentration
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 3 of the sample and on sample preparation. Thus, it
Wait time [s] . . . . . . . . . . 10
Titrant addition . . . . . . . . . . Dynamic is necessary to first determine the potential values
∆E(set)[mV] . . . . . . . . . . 10.0
∆V(min)[mL] . . . . . . . . . . 0.005 for any other mixture.
∆V(max)[mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.3
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
.
.
.
.
.
.
2.0
5.0
Disposal
t(max) [s] . . . . . . . . . . . 52.0
Recognition
Threshold . . . . . . . . .
Steepest jump only . . . .
.
.
.
.
.
.
6.0
No
Neutralization with hydrochloric acid.
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . None
Termination
at maximum volume [mL] . . . . . 12.0 Other titrators
at potential . . . . . . . . . . Yes
Potential [mV, pH,..] . . . . 10.5
at slope . . . . . . . . . . . . No DL50 Graphix, DL53/DL55, DL70ES, DL77.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . .
comb. termination criteria
.
.
.
.
.
.
1
Yes
E-V curve
Evaluation
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . Yes
Pot. 1 [mV, pH,..] . . . . . . 3.75
Potential 2 . . . . . . . . . . . Yes
Pot. 2 [mV, pH,..] . . . . . . 5.5
Stop for reevaluation . . . . . . No
Calculation
Formula . . . . . . . . . . . . . . R=(QP1-(Q-QP2))*C/m
Constant . . . . . . . . . . . . . . C=63.01/(10*z)
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . HNO3 content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=(QP2-QP1)*C2/m
Constant . . . . . . . . . . . . . . C2=60.05/(10*z)
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . HAc content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=(Q-QP2)*C3/m
Constant . . . . . . . . . . . . . . C3=M/(10*z)
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . H3PO4 content
Statistics . . . . . . . . . . . . . Yes
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No Author: Lin Yau Yeng (YY)
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 23/100
METTLER TOLEDO

M153 Nitric, acetic and phosphoric acid mixture: concentrations below 0.3%

Sample: Acid cleaner Instruments: METTLER TOLEDO DL70ES


10 mL Printer EPSON SC600

Substance: Nitric acid, HNO3, 0.1 % Method: Y021


Acetic acid HAc, 0.1%
Phosphoric acid H3PO4, 0.25% Accessories: Titration beakers ME-101974
HNO3 : HAc : H3PO4 = approx. 1 : 1 : 2 Peristaltic pump ME-65241

Preparation: 40 mL deion. water Indication: DG111-SC

Titrant: Sodium hydroxide, NaOH


c(NaOH) = 0.1 mol/L

Standard: Potassium hydrogen phtalate


Results: METTLER DL70ES Titrator V3.1 titration introduction 1998
market support analytical

Method Y021 Mixed Acids-HNO3,H3PO4,HAc Apr/23/1999 10:34 am


User YY
Measured Apr/23/1999 1:36 pm

RESULTS

No ID1 ID2 Sample amount and results

1/1 10.0 mL Fixed volume U


R1 = 0.0935 % Nitric Acid
R2 = 0.1160 % Acetic Acid
R3 = 0.2517 % Phosphoric
1/2 10.0 mL Fixed volume U
R1 = 0.0925 % Nitric Acid
R2 = 0.1179 % Acetic Acid
R3 = 0.2508 % Phosphoric
1/3 10.0 mL Fixed volume U
R1 = 0.0959 % Nitric Acid
R2 = 0.1164 % Acetic Acid
R3 = 0.2501 % Phosphoric

STATISTICS
Number results R1 n = 3
Mean value x = 0.0940 % Nitric Acid
Standard deviation s = 0.001711 % Nitric Acid
Rel. standard deviation srel = 1.821 %

STATISTICS
Number results R2 n = 3
Mean value x = 0.1168 % Acetic Acid
Standard deviation s = 0.001026 % Acetic Acid
Rel. standard deviation srel = 0.878 %

STATISTICS
Number results R3 n = 3
Mean value x = 0.2509 % Phosphoric
Standard deviation s = 0.000804 % Phosphoric
Rel. standard deviation srel = 0.321 %

Page 24/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method Y021 Mixed Acids-HNO3,H3PO4,HAc • This titration procedure includes four steps:
Version Apr/23/1999 10:34 am
1. HNO3 = H+ + NO3-
Title
Method ID . . . . . . . . . . . . . Y021 2. H3PO4 = H+ + H2PO4-
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . Mixed Acids-HNO3,H3PO4,HAc
. . . . Apr/23/1999 10:34 am 3. HAc = H+ + Ac-
Sample
Number samples . . . . . . . . . . 3 4. H2PO4 -
= H+ + HPO42-
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
10.0 Due to the little difference between the pKa-value
Molar mass M . . . . . . . . . . . . 98 of HNO3 and H3PO4 , the first two steps can not be
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . . . . . . Manual distinguished. Therefore only three potential jumps
Stir
Speed [%] . . . . . . . . . . . . . 50 can be seen on the titration curve.
Time [s] . . . . . . . . . . . . . . 10
Titration
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
NaOH
0.1 • The potential jumps are evaluated by means of con-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DG111-SC
mV
trol ranges. To set the optimum values for the con-
Titration mode . . . . . . .
Predispensing 1 . . . . .
.
.
.
.
.
.
.
.
EQP
mL
trol ranges, a trial titration must be first performed.
Volume [mL] . . . . . . . . . 0 From the table of measured values the appropriate
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0 control ranges can be selected and stored in the
Limits ∆V . . . . . . . . . . Absolute
∆V(min) [mL] . . . . . . . 0.05 method.
∆V(min) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU Note that these values depends on the concentra-
∆E [mV] . . . . . . .
∆t [s] . . . . . . .
.
.
.
.
.
.
.
.
0.2
1.0
tion of the sample and on sample preparation. Thus,
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
3.0
30.0
it is necessary to first determine these values for
Threshold . . . . . . . . . . . . 40.0 any other acid mixture.
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 4
Evaluation procedure . .
Calculation
. . . . Standard
Disposal
Result name . . . . . . . . . . . . Nitric Acid
Formula . . . . . . . . . . . . . . R=(Q-Q(EPOT<-100))*C/U
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C=63/(10*z)
%
Neutralization with hydrochloric acid.
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . Acetic Acid
Formula . . . . . . . . . . . . . . R2=Q(100>EPOT>-80)*C2
Constant . . . . . . . . . . . . . . C=60/(U*10*z)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . Phosphoric E-V curve
Formula . . . . . . . . . . . . . . R3=Q(EPOT<-100)*C3/U
Constant . . . . . . . . . . . . . . C=M*3/(10*3)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 4
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes

Other titrators
DL50 Graphix, DL53/DL55, DL77. Author: Lin Yau Yeng (YY)
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 25/100
METTLER TOLEDO

M154 Simultaneous titration of HCl, CH3COOH, and NH4Cl

Sample: 3 mL acid mixture Standard: Potassium hydrogen phtalate


(1 mL of each acid) Instruments: METTLER TOLEDO DL77
Printer EPSON SC600
Substance: Hydrochloric acid HCl, 0.1 mol/L METTLER TOLEDO ST20A
Acetic acid HAc, 0.1 mol/L
Ammonium chloride, NH4Cl, Method: WS2
0.1 mol/L
Accessories: Titration beakers ME-101974
Preparation: 40 mL deion. water Peristaltic pump ME-65241

Titrant: Sodium hydroxide, NaOH Indication: DG111-SC


c(NaOH) = 0.1 mol/L

Results: Sample DG111-1 DG111-2 DG111-3 Theoretical


content
(mg HCl) (mg HCl) (mg HCl) (mg HCl)

1 0.364 0.366 0.366 0.365


2 0.37 0.365 0.367
3 0.373 0.365 0.373
4 0.373 0.367 0.375
5 0.378 0.374 0.371
6 0.372 0.367 0.37

x 0.372 0.367 0.370


s 0.00459 0.00339 0.00344
srel 1.235% 0.922% 0.930%

Sample DG111-1 DG111-2 DG111-3 Theoretical


content
(mg CH3COOH) (mg CH3COOH) (mg CH3COOH) (mg CH3COOH)

1 0.599 0.599 0.602 0.6


2 0.589 0.599 0.602
3 0.577 0.6 0.592
4 0.591 0.598 0.589
5 0.584 0.589 0.594
6 0.593 0.597 0.594

x 0.589 0.597 0.596


s 0.00760 0.00405 0.00536
srel 1.291% 0.678% 0.900%

Sample DG111-1 DG111-2 DG111-3 Theoretical


content
(mg NH4Cl) (mg NH4Cl) (mg NH4Cl) (mg NH4Cl)

1 0.553 0.547 0.55 0.535


2 0.547 0.558 0.565
3 0.575 0.563 0.551
4 0.558 0.555 0.56
5 0.544 0.55 0.547
6 0.553 0.552 0.544

x 0.555 0.554 0.553


s 0.01097 0.00578 0.00804
srel 1.977% 1.042% 1.453%

Page 26/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method WS2 HCl/HOAc/NH4Cl
Version Sep/10/1999 9:49 am

Title
• A mixture of three different acids (hydrochlo-
Method ID . . . . . . . . .
Title . . . . . . . . . . .
. . . . WS2
. . . . HCl/HOAc/NH4Cl
ric acid, acetic acid and ammonium chloride)
Date/time . . . . . . . . .
Sample
. . . . Sep/10/1999 9:49 am
with clear different acid dissociation constant
Number samples . . . . . . .
Titration stand . . . . . .
.
.
.
.
.
.
.
.
6
ST20 1
(pKa = -10, 4.75, and 9.25, respectively) is ti-
Entry type . . . . . . . . .
Lower limit [mL] . . . .
.
.
.
.
.
.
.
.
Volume U
0.5
trated with 0.1 M NaOH.
Upper limit [mL] . . . . . . . . 2.5
ID1 . . . . . . . . . . . . . . . . Serie2
Molar mass M . . . . . . . . . . . . 36.46
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . .
Stir
. . . . Manual
• The mixture is prepared by adding 1 mL 0.1
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 20
mol/L of each acid soution into the titration
Titration
Titrant . . . . . . . . . . . . . . NaOH
beaker. The mixture is diluted with 40 mL
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DG111-SC
deionized water before titration.
Unit of meas. . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EQP
Titrant addition . . . . . . . . DYN
dE(set) [mV] . . . . . . . . . 8.0
Limits dV . . . . . .
dV(min) [mL] . . .
.
.
.
.
.
.
.
.
Absolute
0.03
• Reactions:
dV(max) [mL] . . .
Measure mode . . . . . .
.
.
.
.
.
.
.
.
0.1
EQU
Dominating reaction in the pH-range 2.8-5.0:
dE [mV] . . . . . . .
dt [s] . . . . . . . .
.
.
.
.
.
.
.
.
0.5
1.0
HCl + NaOH = Na + + Cl - + H 2 O
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . .
Maximum volume [mL] . . .
.
.
.
.
.
.
.
.
2.2
4.0
Dominating reaction in the pH-range 5.0-9.0:
Evaluation procedure . .
Stop for reevaluation . .
.
.
.
.
.
.
.
.
Standard
Yes
CH3COOH + NaOH = CH3COO- + Na+ + H2O
Condition . . . . . . . . . . neq=0
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
HCl
R1=Q1*C1/U
Dominating reaction in the pH-range 9.0-11.5:
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C1=M/(10*z)
mg/L
NH4Cl + NaOH = Na+ + Cl- + NH3 + H2O
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . HOAc
Formula . . . . . . . . . . . . . . R2=Q2*C2/U
Constant . . . . . . . . . . . . . . C2=60.0/(10*z)
Result unit . . . . . . . . . . . . mg/L
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
NH4Cl
R3=Q3*C3/U Disposal
Constant . . . . . . . . . . . . . . C3=53.49/(10*z)
Result unit . . . . . . . . . . . . mg/L
Decimal places . . . . . . . . . . . 3
Record Neutralization with hydrochloric acid.
Output unit . . . . . . . . . . . . Printer
Results last sample . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
dE/dV - V curve . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 20.0
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes

Other titrators
DL50 Graphix, DL53/DL55, DL70ES. Authors: H.-J. Muhr, E. Renaud Gueletti, J.Zarske
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 27/100
METTLER TOLEDO

M155 Polishing bath: determination of sulfuric and phosphoric acid

Sample: 1 mL polishing bath Instruments: METTLER TOLEDO DL67


(density: 1.981 g/cm3) Printer EPSON LX400
METTLER TOLEDO ST20A
Substance: Sulfuric acid
Phosphoric acid Method: hpo4

Preparation: - 1:10 dilution Accessories: Titration beakers ME-101974


- 50 mL deion. water Peristaltic pump ME-65241

Titrant: Sodium hydroxide, NaOH Indication: DG111-SC


c(NaOH) = 0.5 mol/L

Standard: Potassium hydrogen phtalate

Results: METTLER DL67 Titrator V3.1

Method hpo4 H2SO4+H3PO4 in Polstar 21-02-1994 10:15


User YY
Measured 21-02-1994 10:42

RESULTS

No ID1 ID2 Sample amount and results

1/1 0.1781 g Weight m


R1 = 49.06 % Phosphoric
R2 = 29.04 % Sulfuric
1/2 0.1781 g Weight m
R1 = 48.89 % Phosphoric
R2 = 29.24 % Sulfuric
1/3 0.1781 g Weight m
R1 = 49.01 % Phosphoric
R2 = 29.38 % Sulfuric

STATISTICS
Number results R1 n = 3
Mean value x = 48.99 % Phosphoric
Standard deviation s = 0.088515 % Phosphoric
Rel. standard deviation srel = 0.181 %

Page 28/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method hpo4 H2SO4+H3PO4 in Polstar • Sample preparation:
Version 21-02-1994 10:15
1 mL polishing bath is first diluted with water
Title (1:10). Again, 1 mL of the diluted solution is add-
Method ID . . . . . . . . . . . . . WS2
Title . . . . . . . . . . . . . . . H2SO4+H3PO4 in Polstar
ed into the titration beaker together with 50 mL
Date/time . . . . . . . . .
Sample
. . . . 21-02-1994 10:15 deionized water.
Number samples . . . . . . . . . . . 3
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Weight m • Sulfuric and phosphoric acid can dissociate two
Lower limit [g] . . . . . . . . . 0.0
Upper limit [mL] . . . . . . . . 2.0 protons H+ (sulfuric acid, H2SO4) and three pro-
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 98 tons H+ (phosphoric acid, H3PO4), respectively.
Equivalent number z . . . . . . . . 1
Temperature sensor . . . . . . . . . Manual The dissociation constants pKa of H2SO4 are:
Stir
Speed [%] . . . . . . . . . . . . . 50 pKa1 = approx. -3,
Time [s] . . . . . . . . . . . . . . 10
Titration pKa2 = 1.92.
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
NaOH
0.5
Sulfuric acid is a strong acid that dissociates com-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DG111-SC
mV
pletely in water.
Titration mode . . . . . . .
Predispensing 1 . . . .
.
.
.
.
.
.
.
.
EQP
mL
The dissociation constants pKa of H3PO4 are:
Volumen [mL] . . . . . . . . 0.1 pKa1 = 2.12
Titrant addition . . . . . . . . DYN
dE(set) [mV] . . . . . . . . . 8.0 pKa2 = 7.21
Limits dV . . . . . . . . . . Absolute
dV(min) [mL] . . . . . . . 0.05 pKa3 = 12.67
dV(max) [mL] . . . . . . . 0.5
Measure mode . . . . . . . . . . EQU In aqueous solution only the first two dissociation
dE [mV] . . . . . . .
dt [s] . . . . . . . .
.
.
.
.
.
.
.
.
0.5
1.0
steps of phosphoric acid can be monitored, while
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
2.0
20.0
the third one is too weak .
Threshold . . . . . . . . . . . . 50.0
Maximum volume [mL] . . . . . . . 30.0
Termination after n EQPs . . . . Yes Based on the pK-values of the two acids in water,
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard the following reactions can be given for the two
Calculation
Result name . . . . . . . . . . . . Phosphoric EQPs found during titration:
Formula . . . . . . . . . . . . . . R1=Q2*C1/m
Constant . . . . . . . . . . . . . . C1=98/(10*z)
Result unit . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
%
2
1st EQP:
Calculation
Result name . . . . . . . . . . . . Sulfuric
H2SO4 + NaOH = Na+ + HSO4- + H2O
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R2=((Q1*2)-(Q1+Q2))*C2
C2=98/(10*z)
HSO4- + NaOH = Na + + SO 4 2- + H 2O
Result unit . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
%
2
H3PO4 + NaOH = H2PO4- + Na+ + H2O
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes 2nd EQP:
=
Rel. standard deviation srel . . . . Yes
Record H2PO4- + NaOH HPO42- + Na+ + H2O
Output unit . . . . . . . . . . . . Printer
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Disposal
Volume [mL] . . . . . . . . . . . . 20.0

Neutralization with hydrochloric acid.

E-V curve

Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Authors: Application Laboratory MT-Germany
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 29/100
METTLER TOLEDO

M156 Determination of boric acid in acidic mixtures of HCl and HF

Sample: Boric acid solution, 5 mL Instruments: METTLER TOLEDO DL70


Printer EPSON FX850
Substance: Hydrochloric acid, HCl with serial interface
Hydrofluoric acid, HF
Boric acid, H3BO3 Method: A001

Preparation: - 30 mL deion. water Accessories: Titration beakers ME-101974


- 20 mL Mannitol solution Additional burette drive DV90
(c(Mannitol) = approx. 200g/L) Additional burette DV1020

Titrant: Sodium hydroxide, NaOH Indication: DG115-SC


c(NaOH) = 0.1 mol/L

Standard: Potassium hydrogen phtalate

Results: METTLER DL70 Titrator

A001 Borsäure measured 14-Nov-1989 12:44


14-Nov-1989 12:28 Titrator
SW Version 1.2 User ****

RESULTS

No Ientification Weight Result

1/1 0.0 g 5.179 mL mL HCl/HF


9.245 mL mL Brsaeure

Page 30/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method A001 Borsäure • Sample preparation:
Version 14-Nov-1989 12:28
200g mannitol are dissolved in 1 L volumetric flask
Title with deion. water.
Method ID . . . . . . . . . . . . . A001
Title . . . . . . . . . . . . . . . Borsäure
Boric acid can not be titrated directly in electro-
Date/time . . . . . . . . .
Sample
. . . . 14-Nov-1989 12:28 plating solution since it is a weak acid. To allow
Number samples . . . . . . . . . . . 1 titration, mannitol is added to the sample. Manni-
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Weight m tol forms a complex with boric acid giving in a me-
Lower limit [mL] . . . . . . . . 0.05
Upper limit [mL] . . . . . . . . 0.15 dium strong acidic compounds.
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 61.83
Equivalent number z . . . . . . . . 1
Stir
• A sample changer ST20A can be used in this meth-
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
od for a fully automatic procedure. The method
Titration can be easily modified for automatic operation:
Titrant . . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . . 0.1 enter "ST20 1" as titration stand in the function
Sensor . . . . . . . . . . . . . . . DG115-SC
Unit of meas. . . . . . . . . . . . mV SAMPLE.
Titration mode . . . . . . . . . . . EP
Predispensing . . . . . . . . . mL
Volume [mL] . . . . . . . . . 1.0
Titrant addition . . . . . . . . Dynamic
• CAUTION: Hydrofluoric acid is poisonous! Work
∆E(set) [mV] . . . . .
∆V(min) [mL] . . . . .
.
.
.
.
.
.
.
.
8.0
0.02
in a fume hood, wear safety goggles and gloves.
∆V(max) [mL] . . . . . . . . . 0.1
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 0.5
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
2.0
20.0
Disposal
Endpoint mode . . . . . . . . . . EPA Neutralization with hydrochloric acid.
Potential [mV,pH,...]. . . . . 0.0
Tendency . . . . . . . . . . . . Negative
Maximum volume [mL] . . . . . . . 10.0
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
mL HCl/HF
R=VEQ[1]
E-V curve:
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mL
Decimal places . . . . . . . . . . . 3 Titration of HCl/HF
Record
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Dispense
Titrant . . . . . . . . . . . . . . Mannitol
Concentration [mol/L] . . . . . . . 0.0
Volume [mL] . . . . . . . . . . . . 20.0
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60
Titration
Titrant . . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DG115-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL
Volumen [mL] . . . . . . . . 1.0
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Absolute
∆V(min) [mL]. . . . . . . . 0.02
∆V(max) [mL]. . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 1.0 Titration of boric acid
∆t [s] . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 20.0
Maximum volume [mL] . . . . . . . 10.0
Evaluation procedure . . . . . . Standard
Calculation
Result name . . . . . . . . . . . . mL Brsaeure
Formula . . . . . . . . . . . . . . R2=VEQ[2]
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mL
Decimal places . . . . . . . . . . . 3
Record
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes

Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Author: Dieter Rehwald
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 31/100
Note:

Determination of nitric and hydrofluoric acid in stainless steel polishing bath

Sample: 1st titration: 0.5 g polishing bath Titrant: Potassium hydroxide, KOH
2nd titration: 1 g polishing bath c(NaOH) = 1.0 mol/L

Substance: Nitric acid, HNO3 Standard: Potassium hydrogen phtalate


Hydrofluoric acid, HF
Instruments: METTLER TOLEDO DL70ES
Preparation: 1st titrationfunction: Printer EPSON FX850
1.1 Weigh 0.5 g of acid sample. with serial interface
1.2 Take 10 mL potassium
fluoride solution (KF, e.g. Method: HF1
10%) and dilute it to 50 mL (This method consists of two
with deionized water. titration functions).
1.3 Add the diluted KF solution
to the sample. Accessories: Titration beakers ME-101974
2nd titration function:
2.1 Weigh 0.5 g of acid sample. Indication: InLab429
2.2 Add 50 mL acetone
2.3 Add 4 g of sodium sulphate

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 deter-
mines 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 (dissocia-
tion constant pKa(HNO3) = -1.32 at 12.5°C; and pKa(HF) = 3.45), they dissociate completely. Since
the pKa values are close to each other, the two potential jumps can not be distinguished during
titration with a strong base in an aqueous solution: there is only one potential jump in the titration
curve.
To discriminate the two potential jumps, the solvent is replaced by acetone, where the difference in
pKa values of the two acids is large enough to separate them. The first EQP of the second titration
function corresponds to nitric acid. Further addition of sodium sulphate, a well-known drying agent
due to its hygroscopic property, allows the achievement of a complete anhydrous environment.
Page 32/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Titration
Titrant . . . . . . . . . . . . . . KOH
Method HF1 HF and HNO3 Content Concentration [mol/L] . . . . . . . 1.0
Version Dec/03/1998 11:25 am Sensor . . . . . . . . . . . . . . . InLab 429
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Title Predispensing 1 . . . . . . . . . mL
Method ID . . . . . . . . . . . . . HF1 Volume [mL] . . . . . . . . . 1.0
Title . . . . . . . . . . . . . . . HF and HNO3 Content Titrant addition . . . . . . . . DYN
Date/time . . . . . . . . . . . . . Dec/03/1998 11:25 am ∆E(set) [mV] . . . . . . . . . 8.0
Sample Limits ∆V . . . . . . . . . . Absolute
Number samples . . . . . . . . . . . 3 ∆V(min) [mL] . . . . . . . 0.02
Titration stand . . . . . . . . . . Stand 1 ∆V(max) [mL] . . . . . . . 0.5
Entry type . . . . . . . . . . . . . Weight m Measure mode . . . . . . . . . . EQU
Lower limit [mL] . . . . . . . . 0.0 ∆E [mV] . . . . . . . . . . . 0.5
Upper limit [mL] . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . 1.0
ID1 . . . . . . . . . . . . . . . . HNO3 t(min) [s] . . . . . . . . . . 3.0
Molar mass M . . . . . . . . . . . . 63.0129 t(max) [s] . . . . . . . . . . 30.0
Equivalent number z . . . . . . . . 1 Threshold . . . . . . . . . . . . 100.0
Temperature sensor . . . . . . . . . Manual Maximum volume [mL] . . . . . . . 20.0
Stir Termination after n EQPs . . . . Yes
Speed [%] . . . . . . . . . . . . . 50 n = . . . . . . . . . . . . . 1
Time [s] . . . . . . . . . . . . . . 30 Termination at slope . . . . . . Yes
Titration Slope [mV,pH,.../mL] . . . . . 50.0
Titrant . . . . . . . . . . . . . . KOH Combined termn criteria . . . . . Yes
Concentration [mol/L] . . . . . . . 1.0 Evaluation procedure . . . . . . Standard
Sensor . . . . . . . . . . . . . . . InLab 429 Steepest jump only . . . . . . . Yes
Unit of meas. . . . . . . . . . . . mV Stop for reevaluation . . . . . . Yes
Titration mode . . . . . . . . . . . EQP Condition . . . . . . . . . . neq=0
Predispensing 1 . . . . . . . . . mL Calculation
Volume [mL] . . . . . . . . . 1.0 Result name . . . . . . . . . . . . HNO3 Content
Titrant addition . . . . . . . . DYN Formula . . . . . . . . . . . . . . R2=Q[2]*C2/m
∆E(set) [mV] . . . . . . . . . 8.0 Constant . . . . . . . . . . . . . . C2=1/z
Limits ∆V . . . . . . . . . . Absolute Result unit . . . . . . . . . . . . mmol/g
∆V(min) [mL] . . . . . . . 0.02 Decimal places . . . . . . . . . . . 4
∆V(max) [mL] . . . . . . . 0.5 Record
Measure mode . . . . . . . . . . EQU Output unit . . . . . . . . . . . . Printer
∆E [mV] . . . . . . . . . . . 0.5 Result last sample . . . . . . . . . Yes
∆t [s] . . . . . . . . . . . . 1.0 Table of values . . . . . . . . . . Yes
t(min) [s] . . . . . . . . . . 3.0 E - V curve . . . . . . . . . . . . Yes
t(max) [s] . . . . . . . . . . 30.0 Statistics
Threshold . . . . . . . . . . . . 100.0 Ri (i=index) . . . . . . . . . . . . R2
Maximum volume [mL] . . . . . . . 20.0 Standard deviation s . . . . . . . . Yes
Termination after n EQPs . . . . Yes Rel. standard deviation srel . . . . Yes
n = . . . . . . . . . . . . . 1 Calculation
Termination at slope . . . . . . Yes Result name . . . . . . . . . . . . HNO3 Content
Slope [mV,pH,.../mL] . . . . . 50.0 Formula . . . . . . . . . . . . . . R3=R2*C3/m
Combined termn criteria . . . . . Yes Constant . . . . . . . . . . . . . . C3=63.0129/(10*z)
Evaluation procedure . . . . . . Standard Result unit . . . . . . . . . . . . %
Steepest jump only . . . . . . . Yes Decimal places . . . . . . . . . . . 3
Stop for reevaluation . . . . . . Yes Calculation
Condition . . . . . . . . . . neq=0 Result name . . . . . . . . . . . . HF Content
Calculation Formula . . . . . . . . . . . . . . R4=(R1-R2)*C4
Result name . . . . . . . . . . . . Total acid Constant . . . . . . . . . . . . . . C4=20.0063/(10*z)
Formula . . . . . . . . . . . . . . R=Q*C/m Result unit . . . . . . . . . . . . %
Constant . . . . . . . . . . . . . . C=1/z Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . mmol/g Record
Decimal places . . . . . . . . . . . 4 Output unit . . . . . . . . . . . . Printer
Record All results . . . . . . . . . . . . Yes
Output unit . . . . . . . . . . . . Printer
Result last sample . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Remarks
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Sample
Number samples . . . . . . . . . . . 3 • A sample changer ST20A can be used in this
Titration stand . . . . . . . . .
Entry type . . . . . . . . . . . .
.
.
Stand 1
Weight m method for a fully automatic procedure. The
Lower limit [mL] . . . . . . .
Upper limit [mL] . . . . . . .
.
.
0.0
1.0 method can be easily modified for automatic
ID1 . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . .
.
.
HF
20.0063 operation: enter "ST20 1" as titration stand in
Equivalent number z . . . . . . .
Temperature sensor . . . . . . . .
.
.
1
Manual the function SAMPLE.
Instruction
Attach sample with sodium sulphate
added and acetone as a solvent
Stir • CAUTION: HF is a very strong acid and it etch-
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60 es glass. Wear gloves and safety goggles.

Disposal

Neutralization with hydrochloric acid.


Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author: Craig Gordon
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 33/100
METTLER TOLEDO

M157 Determination of hydrochloric and nitric acid

Sample: Acid mixture, 1 g Instruments: METTLER TOLEDO DL58


Printer EPSON SC600
Substance: Nitric acid, HNO3 , appr. 25%
Hydrochloric acid, HCl , appr. 3% Methods: jud3:
Determination of total acid
Preparation: method jud3: content.
50 mL deion. water jud2:
method jud2: Determination of hydrochloric
1 mL 10% HNO3 in the sample and nitric acid content.
titrated with method jud3
Accessories: Second burette drive DV90 Sec-
Titrant 1: Sodium hydroxide, NaOH ond burette DV1010
c(NaOH) = 1 mol/L pH Option
Titration beakers ME-101974
Titrant 2: Silver nitrate, AgNO3 Peristaltic pump ME-65241
c(AgNO3) = 1 mol/L
Indication: DG111-SC
Standard: NaOH: Potassium hydrogen phthalate DM141-SC
AgNO3: Sodium chloride

Results: Method jud3 Total acid cont (HCl+HNO3) 08/08/2000 12:20


Measured 08/08/2000 12:32
User J. Maag

ALL RESULTS

No. ID Sample size and results

1 HCl/HNO3 1.011 g
R1 = 29.291 % mmol H+

Method jud2 EQP det. with AgNO3 08/08/2000 12:21


Measured 08/08/2000 12:42
User J. Maag

ALL RESULTS

No. ID Sample size and results

1 HCl/HNO3 1.011 g
R1 = 29.291 % HCl content
R2 = 2.676 % HNO3

Page 34/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method jud3 Method jud2
Method jud3 Total acid cont (HCl+HNO3) Method jud2 HCl det. with AgNO3
Version 08/08/2000 12:20 Version 08/08/2000 12:49

Title Title
Method ID . . . . . . . . . . . . . jud3 Method ID . . . . . . . . . . . . . jud2
Title . . . . . . . . . . . . . Total acid cont Title . . . . . . . . . . . . . HCl det. with AgNO3
(HCl+HNO3) Date/time . . . . . . . . . . . . . 08/08/2000 12:49
Date/time . . . . . . . . . . . . . 08/08/2000 12:20 Sample
Sample Sample ID . . . . . . . . . . . . . HCl/HNO3
Sample ID . . . . . . . . . . . . . HCl/HNO3 Entry type . . . . . . . . . . . . . Weight
Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02
Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0
Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 36.45
Molar mass M . . . . . . . . . . . . 100 Equivalent number z . . . . . . . . 1
Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1
Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . Manual
Temperature sensor . . . . . . . . . Manual Stir
Stir Speed [%] . . . . . . . . . . . . . 50
Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10
Time [s] . . . . . . . . . . . . . . 10 EQP titration
EQP titration Titrant/Sensor
Titrant/Sensor Titrant . . . . . . . . . . . . . AgNO3
Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0
Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DM141
Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . mV
Unit of meas. . . . . . . . . . . pH Predispensing . . . . . . . . . . . No
Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic
Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0
∆E(set)[mV] . . . . . . . . . . 4.0 ∆V(min)[mL] . . . . . . . . . . 0.02
∆V(min)[mL] . . . . . . . . . . 0.01 ∆V(max)[mL] . . . . . . . . . . 0.2
∆V(max)[mL] . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled
Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5
∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0
t(max) [s] . . . . . . . . . . . 30.0 Recognition
Recognition Threshold . . . . . . . . . . . . 1000.0
Threshold . . . . . . . . . . . . 50.0 Steepest jump only . . . . . . . No
Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No
Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . None
Tendency . . . . . . . . . . . . None Termination
Termination at maximum volume [mL] . . . . . 10.0
at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No
at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No
at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes
after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1
n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No
comb. termination criteria . . . No Evaluation
Evaluation Procedure . . . . . . . . . . . . Standard
Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No
Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes
Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0
Condition . . . . . . . . . . neq=0 Calculation
Calculation Formula . . . . . . . . . . . . . . R=Q*C/m
Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . C=M/(10*z)
Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3
Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . %
Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . HCl content
Result name . . . . . . . . . . . . H+ Statistics . . . . . . . . . . . . . No
Statistics . . . . . . . . . . . . . No Calculation
Calculation Formula . . . . . . . . . . . . . . R2=(H5-Q)*C2/m
Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . C2=63.01/(10*z)
Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3
Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . %
Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . HNO3
Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . Yes
Statistics . . . . . . . . . . . . . No Calculation
Auxiliary value Formula . . . . . . . . . . . . . .
ID . . . . . . . . . . . . . . . . . Total acid Constant . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . H5=R Decimal places . . . . . . . . . . . 0
Report Result unit . . . . . . . . . . . .
Output . . . . . . . . . . . . . . . Printer Result name . . . . . . . . . . . .
Results . . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes Report
Raw results . . . . . . . . . . . . Yes Output . . . . . . . . . . . . . . . Printer
Table of measured values . . . . . . Yes Results . . . . . . . . . . . . . . No
Sample data . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes Table of measured values . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No Sample data . . . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No E - V curve . . . . . . . . . . . . Yes
E - t curve . . . . . . . . . . . . No ∆E/∆V - V curve . . . . . . . . . . Yes
V - t curve . . . . . . . . . . . . No ∆2E/∆V2 - V curve . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No

Remarks V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
.
.
.
.
No
No

1. Method jud3: det. of total acid content.


2. Add 1 mL 10% HNO3 for chloride precipitation Disposal
3. Method jud2: determination of HCl by precipita- Filtration/Neutralization with sodium hydroxide.
tion of chloride with AgNO3 Other titrators
4. Difference 1.-2. = content HNO3 DL50 Graphix, DL53/DL55, DL70ES, DL77.
Please note that both methods can be summarized in a
single method. Author: Judy Maag
Electronics and electroplating applications 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 Instruments: METTLER TOLEDO DL58


Printer EPSON SC600
Substance: Ammonia, NH3
Hydrogen peroxide, H2O2 Methods: amm1:
Back titration of NH3
Preparation: method amm1: hydr1:
50 mL deion. water Redox titration of H2O2
method hydr1:
1 mL 10% HNO3 in the sample Accessories: Second burette drive DV90
titrated with method amm1 Second burette DV1010
pH Option
Titrant 1: Sodium hydroxide, NaOH Titration beakers ME-101974
c(NaOH) = 1 mol/L
Indication: DG111-SC
Titrant 2: Nitric acid, HNO3 DM140-SC
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 amm1 Back titration of NH3 08/11/2000 13:29


Measured 08/11/2000 13:31
User J. Maag

ALL RESULTS

No. ID Sample size and results

1 NH3/H2O2 0.662 g
R1 = 3.484 % NH3 Content

Method hydr1 H2O2 determination 08/11/2000 12:50


Measured 08/11/2000 13:37
User J. Maag

ALL RESULTS

No. ID Sample size and results

1 NH3/H2O2 0.662 g
R1 = 0.936 % H2O2 content

Page 36/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method amm1 Method hydr1
Method amm1 Back titration of NH3 Method hydr1 H2O2 determination
Version 08/11/2000 13:29 Version 08/11/2000 12:50

Title Title
Method ID . . . . . . . . . . . . . amm1 Method ID . . . . . . . . . . . . . hydr1
Title . . . . . . . . . . . . . Back titration of NH3 Title . . . . . . . . . . . . . H2O2 determination
Date/time . . . . . . . . . . . . . 08/11/2000 13:29 Date/time . . . . . . . . . . . . . 08/11/2000 12:50
Sample Sample
Sample ID . . . . . . . . . . . . . NH3/H2O2 Sample ID . . . . . . . . . . . . . NH3/H2O2
Entry type . . . . . . . . . . . . . Weight Entry type . . . . . . . . . . . . . Weight
Lower limit [g] . . . . . . . . . 0.02 Lower limit [g] . . . . . . . . . 0.02
Upper limit [g] . . . . . . . . . 2.0 Upper limit [g] . . . . . . . . . 2.0
Molar mass M . . . . . . . . . . . . 17 Molar mass M . . . . . . . . . . . . 34.02
Equivalent number z . . . . . . . . 1 Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Temperature sensor . . . . . . . . . Manual
Dispense Stir
Titrant . . . . . . . . . . . . . . HNO3 Speed [%] . . . . . . . . . . . . . 50
Concentration [mol/L] . . . . . . . 2.0 Time [s] . . . . . . . . . . . . . . 10
Volume [mL] . . . . . . . . . . . . 4.5 EQP titration
Stir Titrant/Sensor
Speed [%] . . . . . . . . . . . . . 50 Titrant . . . . . . . . . . . . . 1/5 KMnO4
Time [s] . . . . . . . . . . . . . . 10 Concentration [mol/L] . . . . . . 0.1
EQP titration Sensor . . . . . . . . . . . . . DM140
Titrant/Sensor Unit of meas. . . . . . . . . . . mV
Titrant . . . . . . . . . . . . . NaOH Predispensing . . . . . . . . . . . No
Concentration [mol/L] . . . . . . 1.0 Titrant addition . . . . . . . . . . Dynamic
Sensor . . . . . . . . . . . . . DG111 ∆E(set)[mV] . . . . . . . . . . 8.0
Unit of meas. . . . . . . . . . . pH ∆V(min)[mL] . . . . . . . . . . 0.02
Predispensing . . . . . . . . . . . No ∆V(max)[mL] . . . . . . . . . . 0.2
Titrant addition . . . . . . . . . . Dynamic Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E(set)[mV] . . . . . . . . . . 8.0 ∆E [mV] . . . . . . . . . . . . . 0.5
∆V(min)[mL] . . . . . . . . . . 0.02 ∆t [s] . . . . . . . . . . . . . 1.0
∆V(max)[mL] . . . . . . . . . . 0.2 t(min) [s] . . . . . . . . . . . 3.0
Measure mode . . . . . . . . . . . . Equilibrium controlled t(max) [s] . . . . . . . . . . . 15.0
∆E [mV] . . . . . . . . . . . . . 0.5 Recognition
∆t [s] . . . . . . . . . . . . . 1.0 Threshold . . . . . . . . . . . . 2000.0
t(min) [s] . . . . . . . . . . . 3.0 Steepest jump only . . . . . . . No
t(max) [s] . . . . . . . . . . . 30.0 Range . . . . . . . . . . . . . . No
Recognition Tendency . . . . . . . . . . . . Positive
Threshold . . . . . . . . . . . . 100.0 Termination
Steepest jump only . . . . . . . No at maximum volume [mL] . . . . . 8.0
Range . . . . . . . . . . . . . . No at potential . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive at slope . . . . . . . . . . . . No
Termination after number EQPs . . . . . . . . Yes
at maximum volume [mL] . . . . . 10.0 n = . . . . . . . . . . . . . 1
at potential . . . . . . . . . . No comb. termination criteria . . . No
at slope . . . . . . . . . . . . No Evaluation
after number EQPs . . . . . . . . Yes Procedure . . . . . . . . . . . . Standard
n = . . . . . . . . . . . . . 1 Potential 1 . . . . . . . . . . . No
comb. termination criteria . . . No Potential 2 . . . . . . . . . . . No
Evaluation Stop for reevaluation . . . . . . Yes
Procedure . . . . . . . . . . . . Standard Condition . . . . . . . . . . neq=0
Potential 1 . . . . . . . . . . . No Calculation
Potential 2 . . . . . . . . . . . No Formula . . . . . . . . . . . . . . R=Q*C/m
Stop for reevaluation . . . . . . Yes Constant . . . . . . . . . . . . . . C=M/(10*z)
Condition . . . . . . . . . . neq=0 Decimal places . . . . . . . . . . . 3
Calculation Result unit . . . . . . . . . . . . %
Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m Result name . . . . . . . . . . . . H2O2 content
Constant . . . . . . . . . . . . . . C=M/(10*z) Statistics . . . . . . . . . . . . . Yes
Decimal places . . . . . . . . . . . 3 Calculation
Result unit . . . . . . . . . . . . % Formula . . . . . . . . . . . . . .
Result name . . . . . . . . . . . . NH3 Content Constant . . . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Decimal places . . . . . . . . . . . 0
Calculation Result unit . . . . . . . . . . . .
Formula . . . . . . . . . . . . . . Result name . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Statistics . . . . . . . . . . . . . No
Decimal places . . . . . . . . . . . 0 Calculation
Result unit . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Result name . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Decimal places . . . . . . . . . . . 0
Report Result unit . . . . . . . . . . . .
Output . . . . . . . . . . . . . . . Printer Result name . . . . . . . . . . . .
Results . . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes Report
Raw results . . . . . . . . . . . . No Output . . . . . . . . . . . . . . . Printer
Table of measured values . . . . . . Yes Results . . . . . . . . . . . . . . No
Sample data . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes Table of measured values . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No Sample data . . . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No E - V curve . . . . . . . . . . . . Yes
E - t curve . . . . . . . . . . . . No ∆E/∆V - V curve . . . . . . . . . . Yes
V - t curve . . . . . . . . . . . . No ∆2E/∆V2 - V curve . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Remarks
Disposal
1. Method amm1: det. of NH3 by back titration. The sample has to be classified as special waste.
2. Add 1 mL 10% HNO3 for peroxide determination
3. Method hydr1: determination of HCl by redox ti-
tration with 1/5 KMnO4. Other titrators
Please note that both methods can be resumed in a sin- DL50 Graphix, DL53/DL55, DL70ES, DL77.
gle method. Author: Judy Maag
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 37/100
METTLER TOLEDO

M159 Determination of hydrochloric acid and hydrogen peroxide

Sample: Acid mixture, 0.5-1 g Instruments: METTLER TOLEDO DL58


Printer EPSON SC600
Substance: Hydrochloric acid, HCl
Hxdrogen peroxide, H2O2 Methods: hcl1:
Titration of HCl
Preparation: method hcl1: hydr1:
50 mL deion. water Redox titration of H2O2
method hydr1:
1 mL 10% HNO3 in the sample Accessories: Second burette drive DV90
titrated with method hcl1 Second burette DV1010
pH Option
Titrant 1: Sodium hydroxide, NaOH Titration beakers ME-101974
c(NaOH) = 1 mol/L
Indication: DG111-SC
Titrant 2: Potassium permanganate, KMnO4 DM140-SC
c(1/5 KMnO4) = 0.1 mol/L

Standard: NaOH: Potassium hydrogen phthalate


KMnO4: sodium oxalate, Na2C2O4

Results: Method hcl1 Back titration of NH3 08/11/2000 14:01


Measured 08/11/2000 14:03
User J. Maag

ALL RESULTS

No. ID Sample size and results

1 HCl/H2O2 0.777 g
R1 = 1.188 % HCl Content

Method hydr1 H2O2 determination 08/11/2000 14:03


Measured 08/11/2000 14:07
User J. Maag

ALL RESULTS

No. ID Sample size and results

1 HCl/H2O2 0.777 g
R1 = 2.075 % H2O2 content

Page 38/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method hcl1 Method hydr1
Method hcl1 Titration of HCl Method hydr1 H2O2 determination
Version 08/11/2000 14:01 Version 08/11/2000 14:03

Title Title
Method ID . . . . . . . . . . . . . hcl1 Method ID . . . . . . . . . . . . . hydr1
Title . . . . . . . . . . . . . Titration of HCl Title . . . . . . . . . . . . . H2O2 determination
Date/time . . . . . . . . . . . . . 08/11/2000 14:01 Date/time . . . . . . . . . . . . . 08/11/2000 14:03
Sample Sample
Sample ID . . . . . . . . . . . . . HCl/H2O2 Sample ID . . . . . . . . . . . . . HCl/H2O2
Entry type . . . . . . . . . . . . . Weight Entry type . . . . . . . . . . . . . Weight
Lower limit [g] . . . . . . . . . 0.02 Lower limit [g] . . . . . . . . . 0.02
Upper limit [g] . . . . . . . . . 2.0 Upper limit [g] . . . . . . . . . 2.0
Molar mass M . . . . . . . . . . . . 36.35 Molar mass M . . . . . . . . . . . . 34.02
Equivalent number z . . . . . . . . 1 Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Temperature sensor . . . . . . . . . Manual
Stir Stir
Speed [%] . . . . . . . . . . . . . 50 Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 Time [s] . . . . . . . . . . . . . . 10
EQP titration EQP titration
Titrant/Sensor Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH Titrant . . . . . . . . . . . . . 1/5 KMnO4
Concentration [mol/L] . . . . . . 1.0 Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DG111 Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . pH Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No Predispensing . . . . . . . . . . . No
Titrant addition . . . . . . . . . . Dynamic Titrant addition . . . . . . . . . . Dynamic
∆E(set)[mV] . . . . . . . . . . 8.0 ∆E(set)[mV] . . . . . . . . . . 8.0
∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(min)[mL] . . . . . . . . . . 0.02
∆V(max)[mL] . . . . . . . . . . 0.2 ∆V(max)[mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.5 ∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0 t(max) [s] . . . . . . . . . . . 15.0
Recognition Recognition
Threshold . . . . . . . . . . . . 100.0 Threshold . . . . . . . . . . . . 2000.0
Steepest jump only . . . . . . . No Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive Tendency . . . . . . . . . . . . Positive
Termination Termination
at maximum volume [mL] . . . . . 10.0 at maximum volume [mL] . . . . . 8.0
at potential . . . . . . . . . . No at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No comb. termination criteria . . . No
Evaluation Evaluation
Procedure . . . . . . . . . . . . Standard Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 Condition . . . . . . . . . . neq=0
Calculation Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) Constant . . . . . . . . . . . . . . C=M/(10*z)
Decimal places . . . . . . . . . . . 3 Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . % Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . HCl Content Result name . . . . . . . . . . . . H2O2 content
Statistics . . . . . . . . . . . . . Yes Statistics . . . . . . . . . . . . . Yes
Calculation Calculation
Formula . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
Calculation Calculation
Formula . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
Report Report
Output . . . . . . . . . . . . . . . Printer Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No Raw results . . . . . . . . . . . . Yes
Table of measured values . . . . . . Yes Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes ∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No ∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No ∆V/∆t - t curve . . . . . . . . . . No

Remarks Disposal
The sample to be classified as special waste.
1. Method hcl1: det. of HCl by direct titration.
2. Add 1 mL 10% HNO3 for peroxide determination
3. Method hydr1: determination of H2O2 by redox Other titrators
titration with 1/5 KMnO4. DL50 Graphix, DL53/DL55, DL70ES, DL77.
Note: the methods can be resumed in a single one. Author: Judy Maag
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 39/100
METTLER TOLEDO

M181 Back-titration of aluminum in acidic bath

Sample: Acid mixture, 1 mL Instruments: METTLER TOLEDO DL58


Printer
Substance: Aluminium, Al, 15 g/L
Sulfuric acid, H2SO4 Methods: 40001
Oxalic acid, H2C2O4
Accessories: Glass beakers ME-101446
Preparation: 1. 20 mL deion. water Additional DV1020 burette
2. 20 mL buffer solution pH 4
3. Dispense exactly 20 mL Indication: - Hg-DM141
0.1 mol/L EDTA (Amalgamated DM141)
4. Warm up during 10 min.
until boiling point. - 3 drops 0.05 mol/L HgEDTA

Titrant: Zinc sulfate, ZnSO4


c(ZnSO4) = 0.1 mol/L

Standard: ZnSO4: EDTA Standard


EDTA: ZnSO4 Standard

Results: Sample Al content Comments

Acidic bath (g/L)

n = 4 flat titration
curve
x 15.434
srel 0.66% DL40 Appl. no. 315

Sample Al Purity Comments

KAl(SO4)2•12 H2O (%)

n = 5 INC = 0.1 mL
Threshold= 100mV/mL
x 99.542 ∆E = 0.5 mV
srel 0.05% ∆t = 3.0
DL40 Appl. no. 110

Page 40/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40001 Aluminium
Version 11/01/2001 16:30 Aluminium acidic bath (Elox bath)
Title
Method ID . . . . . . . . . . . . . 40001 • This acidic bath contains aluminium, sulfuric and
Title . . . . . . . . . . . . . Aluminium
Date/time . . . . . . . . . . . . . 11/01/2001 16:30 oxalic acid.
Sample
Sample ID . . . . . . . . . . . . . Al/H2SO4/C2O42- • The method was developed on the DL40 titrator
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . . . . . . 1.0 (see DL40 applications No. 3, 110, 315) and has
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
26.982
1
been adapted for the DL5x- and DL7x-titrators.
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50
Sample preparation
Time [s] . . . . . . . . . . . . . . 10
EQP titration 1) Add 20 mL deionized water to the sample.
Titrant/Sensor
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
ZnSO4
0.1
2) Add 20 mL buffer solution pH 4 to avoid formation
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
HgDM141
mV
of aluminium hydroxide.
Predispensing . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 5.0 3) 20 mL 0.1 mol/L EDTA are dispensed using the
Titrant addition . . . . . . . . . . INC
∆V [mL] . . . . . . . . . . . . . 0.3 auxiliary function "Dosing" of the titrator.
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 3.0 4) The sample beaker is heated to boiling during 10
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0 minutes since the complexation of aluminium with
Recognition
Threshold . . . . . . . . . . . . 25.0 EDTA is very slow at room temperature. Cover the
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
glass titration beaker during heating.
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . . . . . 20.0
5) Add three drops 0.05 mol/L Hg-EDTA
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 Procedure
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard • The aluminum concentration is determined by a
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No back titration of excess EDTA with zinc sulfate.
Stop for reevaluation . . . . . . Yes

Calculation
Condition . . . . . . . . . . neq=0 • A blank titration is performed before analysis. The
Formula . . . . . . . . . . . . . . R=(H1-Q)*C/m result (mmol) is stored as auxiliary value H1 and
Constant . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 3 used for the back-titration.
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Al Content
Yes
• The EDTA excess is titrated with method 40001.
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
Chemicals
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . • Buffer solution pH 4: Dissolve 120 mL glacial ace-
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No tic acid (i.e. 100%) and 54 g sodium acetate trihy-
Calculation
Formula . . . . . . . . . . . . . . drate in a 1 L flask. Add 10 mL 0.05 mol/L HgED-
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 TA, and dilute to 1 L with deionized water.
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No • 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
Report
Output . . . . . . . . . . . . . . . Printer
and 0.05 mol/L Hg-acetate are mixed together. This
Results . . . . . . . . . . .
All results . . . . . . . . .
.
.
.
.
.
.
No
Yes
solution is used as an indicator for the titration and
Raw results . . . . . . . . .
Table of measured values . . .
.
.
.
.
.
.
No
Yes
is dissolved into the buffer solution instead of add-
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
.
.
.
.
.
.
No
Yes
ing three drops for each sample.
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No Amalgamation of DM141 electrode (HgDM141)
∆V/∆t - t curve . . . . . . . . . . No

• 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
Disposal excess mercury is wiped off. Several titrations can
The sample to be classified as special waste (Hg).
be indicated before re-amalgamation.
• Note: the Hg-DM141 is inactivated by hydrogen
Other titrators
peroxide, H2O2, and by S2-, CN- , .... .
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 41/100
METTLER TOLEDO

M182 Titration of sulphuric acid and aluminum in an electroplating bath

Sample: Acidic bath, 2 mL Instruments: METTLER TOLEDO DL53


Epson matrix printer LX800
Substance: Free sulfuric acid, H2SO4 with serial inteface 8148
(M = 98 ; z = 2)
Aluminium, Al(III) Method: 25002
(M = 26.98 ; z = 3)
Accessories: Titration beakers ME-101974
Preparation: 50 mL deionized water
Indication: DG111-SC
Titrant: Sodium hydroxide, NaOH:
c(NaOH) = 1 mol/L

Standard: Potassium hydrogen phtalate


(see application M531)

Results:
Results n srel Comments

Content (g/L) Free acid


as H2SO4:
287.180 g/L 4 0.134%

Content Aluminum:
1.857 g/L 3 1.323%

Test solution:

Content (g/L) Free acid Test solution:


as H2SO4:
49.042 g/L 5 0.219% 2 mL 1 mol/L H2SO4
+ 2 mL Al2(SO4)3 2.3 g/L Al

Theoretical 49 g/L
content (g/L)

Content Aluminum:
2.347 g/L 5 1.233%

Theoretical
content (g) 2.3 g/L Al

Page 42/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 25002 Free acid + Al
Version 26/01/2001 15:46
• The method was developed on the DL25 titrator
Title
Method ID . . . . . . . . . . . . . 25002
and has been adapted for the DL5x-/7x-titrators.
Title . . . . . . . . . . . . . Free acid + Al
Date/time . . . . . . . . . . . . . 26/01/2001 15:46
Sample
Sample ID . . . . . . . . . . . . . H2SO4/Al
Procedure
Entry type . . . . . . . . . . . . . Fixed volume • The determination of free acid and aluminum in an
Volume [mL] . . . . . . . . . . . 2.0
Molar mass M . . . . . . . . . . . . 26.98 acidic aluminun bath is determined with a single
Equivalent number z . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1 titration using sodium hydroxide.
Temperature sensor . . . . . . . . . Manual
Stir • The titration curve gives three equivalence points:
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
EQP titration
Titrant/Sensor 1st EQP: Neutralization of free acid
Titrant . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . 1.0 H2SO4 + 2 NaOH = Na2SO4 + 2 H2O
Sensor . . . . . . . . . . . . . DG111
Unit of meas. . . . . . . . . . . As installed
Predispensing . . . . . .
Titrant addition . . . . .
.
.
.
.
.
.
.
.
.
.
No
Dynamic
2nd EQP: Precipitation of aluminum hydroxide
∆E(set) [mV] . . . . . . . . . . 4.0 Al2(SO4)3 + 6 NaOH = 2 Al(OH)3 + 2 H2O
∆V(min) [mL] . . . . . . . . . . 0.02
∆V(min) . . . . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . .
∆t [s] . . . . . . . .
.
.
.
.
.
.
.
.
.
.
0.5
1.0
3rd EQP: Dissolution of Al(OH)3
t(min) [s] . . . . . . . . . . . 3.0 Al(OH)3 + NaOH = Al(OH)4- + Na+
t(max) [s] . . . . . . . . . . . 30.0
Recognition
Threshold . . . . . . . . . . . . 4
Steepest jump only . .
Range . . . . . . . . .
.
.
.
.
.
.
.
.
.
.
No
No
Literature
Tendency . . . . . . . . . . . . Positive
Termination • Application no. M531, in Application brochure 18,
at maximum volume [mL] . . . . . 4.0
at potential . . . . . . . . . . No "Standardization of Titrants", 2000.
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . No
Evaluation
Procedure . . . . . . .
Potential 1 . . . . . .
.
.
.
.
.
.
.
.
.
.
Standard
No Titration curves: standard solution
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0
Calculation
Formula . . . . . . . . . . . . . . R1=Q1*C1/m
Constant . . . . . . . . . . . . . . C1=98.07/2
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . H2SO4
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=Q2*C2/m
Constant . . . . . . . . . . . . . . C2=M/z
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Aluminum
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Neutralization with HCl, special waste

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Author: Roland Böhlen, MT-Switzerland
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 43/100
METTLER TOLEDO

M183 Determination of nickel and cadmium by complexometry

Sample: Standard solutions, 5 mL Instruments: METTLER TOLEDO DL58


Printer
Substance: Cadmium, Cd
Nickel, Ni Methods: 40002

Preparation: A) Only Cd, masking of Ni: Accessories: Titration beakers ME-101974


- 10 mL buffer pH 10 solution DV1010 burette
- 0.5 g dimethyl glyoxime,
sodium salt octahydrate Indication: - Hg-DM141
(C4H6N2Na2O2 • 8 H2O) (Amalgamated DM141)
- 40 mL deionized water
- 3 drops 0.05 mol/L HgEDTA
B) Ni, Cd, Ni + Cd: for each sample.
- 10 mL buffer pH 10 solution
- 40 mL deionized water

Titrant: EDTA, e.g. c(EDTA) = 0.1 mol/L

Standard: ZnSO4

Results:

Sample Titrant Increment Result n srel Comments


mol/L mL g/L %

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 0.1 0.1 5.731(Cd) 5 0.22 Steep titration curve


1 : 1 0.1 2.921 (Ni) 5 --

Ni + Cd 0.1 0.1 11.618 (Cd) 2 -- Steep titration curve


1 : 1 0.1 0.1 5.8060 (Ni) 4 --

Ni + Cd 0.1 0.05 11.33 (Cd) 5 0.12


1 : 100 0.1 0.061 (Ni) 5 -- Less accurate result

Ni + Cd 0.01 0.05 0.1124 (Cd) 5 1.82 Curve less steep (Cd)


100: 1 0.1 5.768 (Ni) 5 --

Cd Stand. 0.01 0.05 Titerfactor 4 0.69


solution 0.8944

Page 44/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40002 Ni + Cd
Version 12/01/2001 15:50 • The method was developed on the DL40 titrator
Title (see DL40 applications No. 317) and has been
Method ID . . . . . . . . . . . . . 40002
Title . . . . . . . . . . . . . Ni + Cd adapted for the DL5x- and DL7x-titrators.
Date/time . . . . . . . . . . . . . 12/01/2001 15:50
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Ni/Cd
Fixed volume Sample preparation
Volume [mL] . . . . . . . . . . . 5.0
Molar mass M . . . . . . . . . . . . 112.41 A) Cadmium determination:
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 1) Add 10 mL buffer solution pH 10.
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50
2) Add 0.5 g dimethylglyoxime disodium salt to
Time [s] . . . . . . . . . . .
EQP titration
. . . 10
mask nickel ions.
Titrant/Sensor
Titrant . . . . . . . . . . . . . EDTA 3) Add 40 mL deionized water.
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . HgDM141 4) Add 3 drops 0.05 mol/L HgEDTA.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 1.0 B) Ni determination:
Titrant addition . . . . . . . . . . INC
∆V [mL] . . . . . . . . . . . . . 0.1 1) Add 10 mL buffer solution pH 10.
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
0.2
2.0
2) Add 40 mL deionized water.
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0 3) Add 3 drops 0.05 mol/L HgEDTA.
Recognition
Threshold . . . . . . . . . . . . 150
Steepest jump only . . . . . . . No
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Negative Procedure
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
20.0
No
• Cd content:
at slope . . . . . . . . .
after number EQPs . . . . .
.
.
.
.
.
.
No
Yes
1) Ni is masked with dimethylglyoxime disodium
n = . . . . . . . . . .
comb. termination criteria
.
.
.
.
.
.
1
No
salt. The sample is titrated with method 40002.
Evaluation
Procedure . . . . . . . . . . . . Standard
2) The Cd content is stored as auxiliary value H6.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . .
Condition . . . . . . .
.
.
.
.
.
.
Yes
neq=0
• Ni content:
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
1) EDTA forms complexes with both Ni and Cd.
Constant . . . . . . . . . . . . . . C=M/z 2) To distinguish both metal ions, the Cd content
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . . . . . g/L is accounted for as a blank value in the calcula-
Result name . . . . . . . . . . . . Cd Content
Statistics . . . . . . . . . . . . . Yes tion: R = (Q - H6)*C/m .
Calculation
Formula . . . . . . . . . . . . . . R2=Q 3) Since nickel is determined, C = M(Ni)/z, and
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3 therefore M = 58.59 .
Result unit . . . . . . . . . . . . mmol
Result name . . . . . . . . . . . . Cd Content
Statistics . . . . . . . . . . . . . Yes
Auxiliary value Chemicals
ID . . . . . . . . . . . . . . . . . mmol Cd
Constant . . . . . . . . . . . . . . H6=R2
Report • Buffer solution pH 10: 70 mL of concentrated am-
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No
monia solution (d=0.9 g/mL) and 70 g ammonium
All results . . . . . . . . .
Raw results . . . . . . . . .
.
.
.
.
.
.
Yes
No
chloride (or 110 g NH4NO3) are dissolved in a 1 L
Table of measured values . . .
Sample data . . . . . . . . .
.
.
.
.
.
.
Yes
No
flask with deionized water.
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No and 0.05 mol/L Hg-acetate are mixed together.
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Amalgamation of DM141 electrode (HgDM141)


• 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
Disposal excess mercury is wiped off. Several titrations can
The sample to be classified as special waste (Hg). be indicated before re-amalgamation.
• Note: the Hg-DM141 is inactivated by hydrogen
Other titrators peroxide, H2O2, and by S2-, CN- , .... .
DL50 Graphix, DL53/DL55, DL70ES, DL77.
Author: Kees Mooibroek
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 45/100
METTLER TOLEDO

M184 Determination of cadmium in alkaline baths

Sample: 1 mL alkaline bath Instruments: METTLER TOLEDO DL67


Printer EPSON LX400
Substance: Cadmium, Cd METTLER TOLEDO ST20A

Preparation: - 50 mL deion. water. Method: BL65


- 0.25 g 1:500 Murexide:NaCl
trituration Accessories: Titration beakers ME-101974
Peristaltic pump ME-65241
Titrant: EDTA
c(EDTA) = 0.1 mol/L Indication: DP660 Phototrode at sensor 2
with
Standard: 0.1 mol/L ZnSO4 DIN-Lemo adapter ME-89600

Results:

Method BL65 Cadmium im alk. Elektrolyt 21-02-1994 9:48


User
Measured 28-02-1994 9:57

RESULTS

No ID1 ID2 Sample amount and results

1/1 1.0 mL Fixed volume U


R1 = 24.06 g/L Cadmium
1/2 1.0 mL Fixed volume U
R1 = 23.08 g/L Cadmium
1/3 1.0 mL Fixed volume U
R1 = 24.04 g/L Cadmium

STATISTICS
Number results R1 n = 3
Mean value x = 23.73 g/L Cadmium
Standard deviation s = 0.560119 g/L Cadmium
Rel. standard deviation srel = 2.361 %

Page 46/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method BL65 Cadmium im alk. Elektrolyt
Version 21-02-1994 9:48

Title
Sample preparation
Method ID . . . . . . . . . . . . . BL65
Title . . . . . . . . . . . . . . . Cadmium im alk.
1) The sample is diluted and then titrated with 0.1 M
Elektrolyt EDTA. No pH buffer is added, the bath is alkaline.
Date/time . . . . . . . . . . . . . 21-02-1994 9:48
Sample
Number samples . . . . . . . . . . . 3
2) Use a trituration 1:500 murexide: NaCl.
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume U 3) Add the indicator before starting analysis. Keep
Volume [mL] . . . . . . . . . . . 1.0
ID1 . . . . . . . . . . . . . . . . sample free of air bubbles during titration. Air
Molar mass M . . . . . . . . . . . . 112.40
Equivalent number z . . . . . . . . 1 bubbles and undissolved impurities affect with the
Temperature sensor . . . . . . . . . Manual
Stir photometric indication.
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 4) Adjust the DP660 at 1000 mV in deionised water
Titration
Titrant . . . . . . . . . . . . . . EDTA before starting titration (100% transmission).
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DP660
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . mL
Volume [mL] . . . .
Titrant addition . . . .
.
.
.
.
.
.
.
.
0.5
DYN
Titration
dE(set) [mV] . . . . . . . . . 8.0
Limits dV . . . . . . . . . . Absolute • Cd(II) ions forms complexes with the indicator
dV(min) [mL] . . . . . . . 0.05
dV(max) [mL] . . . . . . . 0.2 murexide in alkaline:
Measure mode . . . . . . . . . . EQU
dE [mV] . . . . . . . . . . . 0.5
dt [s] . . . . . . . .
t(min) [s] . . . . . .
.
.
.
.
.
.
.
.
1.0
3.0
Cd 2+ + Murexide - = Cu-Murexid +
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 50.0
Maximum volume [mL] . . . . . . . 20.0 • By titration with EDTA, Murexide is diplaced by
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 EDTA and forms a complex with Cd ions in an
Evaluation procedure . . . . . . Asymmetric
Rinse alkaline, neutral or weakly acid medium:
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Calculation
Result name . . . . . . . . . . . . Cadmium
Cd 2+ + H2-EDTA2- = Cd-EDTA2- + 2 H+
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C1=M/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . .
Rel. standard deviation srel
. . . . Yes
. . . . Yes Disposal
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Special waste

Application note:
Determination of Cd in a Cd-Ag alloy
Sample: 1.5 g Cd-Ag Alloy
Preparation: Add 20 mL HNO3 , boil to dissolve , cool
to room temperature, fill up to 100 mL with deionized
E-V curve
water. To aliquots of 5 mL add 10 mL buffer ph 4.5
solution and 5 drops HgEDTA
Indication: HgDM141, HgEDTA
Titrant: EDTA, c(EDTA)=0.1 mol/L
Titration parameter: INC (0.1 mL), EQU (0.5 mV/2 s)
Calculation: Q*C/m; C = M/(10*z), M = 112.40
Literature: DL40 application note 1986, Appl. Data-
base 40.8603

Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Authors: Application Laboratory MT-Germany
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 47/100
METTLER TOLEDO

M185 Iodometric titration of Cr(VI) in an electroplating bath

Sample: Chromium (VI) bath, 0.1 mL Instruments: METTLER TOLEDO DL70


(diluted/aliquot, see sample prepa- METTLER TOLEDO ST20A
ration) METTLER TOLEDO AT261
Printer EPSON FX850
Substance: Cr(VI) as CrO3 with serial interface
M = 99.99 ; z = 3
Method: vd03
Preparation: - 50 mL deionized water
- Sulfuric acid 1:1, 10 mL Accessories: Titration beakers ME-101974
- Potassium iodide, KI, 1.5 g Peristaltic pump SP40

Titrant: Sodium thiosulphate, Na2S2O3 Indication: DM140 at sensor 2


c(Na2S2O3)=0.1 mol/L

Standard: Potassium iodate, KIO3

Results: METTLER DL70 Titrator

vd03 Chromium (VI) measured 23-Nov-1989 12:32


23-Nov-1989 12:04 Titrator Mettler Tiel
SW Version 1.2 User 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 Identification Volume Results

1/1 0.1 mL 149.94 g/L CrO3


1/2 0.1 mL 150.01 g/L CrO3
1/3 0.1 mL 150.08 g/L CrO3
1/4 0.1 mL 151.52 g/L CrO3
1/5 0.1 mL 150.41 g/L CrO3
1/6 0.1 mL 150.27 g/L CrO3
1/7 0.1 mL 150.06 g/L CrO3
1/8 0.1 mL 149.64 g/L CrO3

STATISTICS
Number results R1 n = 8
Mean value x = 150.24 g/L CrO3
Standard deviation s = 0.565 g/L CrO3
Rel. standard deviation srel = 0.376 %

Page 48/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method vd03 Chromium (VI) in Cr-bath Sample preparation
Version 23-Nov-1989 12:04
1) 1 mL chromium bath is diluted with deionized
Title water to 10 mL. 1 mL aliquot corresponds to 0.1
Method ID . . . . . . . . . . . . . vd03
Title . . . . . . . . . . . . . . . Chromium (VI) in Cr-bath mL original sample.
Date/time . . . . . . . . . . . . . 23-Nov-1989 12:04
Sample 2) 1 mL aliquot is diluted with 20 mL deion. water.
Number samples . . . . . . . . . . . 8
Titration stand . . . . . . . . . . ST20 3) 10 mL sulfuric acid 1:1 are added.
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1 4) Add 1.5 g potassium iodide (KI) and cover the bea-
Molar mass M . . . . . . . . . . . . 99.99 kers to avoid loss of iodine.
Equivalent number z . . . . . . . . 3
Stir
Speed [%] . . . . . . . . . . . . . 60
5) The sample solution is kept in the dark during 5-10
Time [s] . . . . . . . . . .
Titration
. . . . 10 minutes.
Titrant . . . . . . . . . . . . . . Na2S2O3
Concentration [mol/L] . . . . . . . 0.1 6) During this time, Cr(VI) is reduced by excess io-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DM140-SC
mV
dide (I-) to Cr(III):
Titration mode . . . . . . .
Predispensing . . . . .
.
.
.
.
.
.
.
.
EP
mL 2 Cr6+ + 6 I - → 2 Cr3+ + 3 I2 (z = 3)
Volume [mL] . . . . . . . . . 2.0
Titrant addition . . . . . . . . DYN The amount of iodine I2 formed is proportional to
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V [mL] . . . . . . . . Absolute the Cr(VI) content.
∆V(min) [mL] . . . . . . . 0.02
∆V(max) [mL] . . . . . . . 0.2 Titration of iodine
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 The formed I2 is then titrated with Na2S2O3:
∆t [s] . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 300.0 2 S2O32- + I2 → S4O62- + 2 I-
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard • Stir moderately. Vigorous stirring causes loss of I2
Calculation
Result name . . . . . . . . . . . . CrO3
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=Q*C/U
C=M/z
Table of measured values:
Result unit . . . . . . . . . . . . g/L
Volume Increment Signal Change 1st deriv. Time
Decimal places . . . . . . . . . . . 2
mL mL mV mV mV/mL min:s
Rinse
Auxiliary reagent . . . . . . . . . H2O
E1 0.000 298.6 0:03
Volume [mL] . . . . . . . . . . . . 10.0
1.143 1.143 296.6 -2.0 -1.8 0:09
Statistics
1.714 0.571 295.1 -1.5 -2.5 0:14
Ri (i=index) . . . . . . . . . . . . R1
E2 2.000 0.286 294.1 -1.0 -3.6 0:19
Standard deviation s . . . . . . . . Yes
2.200 0.200 293.3 -0.8 -4.2 0:23
Rel. standard deviation srel . . . . Yes
2.400 0.200 292.4 -0.8 -4.1 0:28
Record
2.600 0.200 291.4 -1.0 -5.2 0:35
Short-form method . . . . . . . . . Yes
2.800 0.200 290.2 -1.2 -6.2 0:40
Results last sample . . . . . . . . Yes
3.000 0.200 288.7 -1.4 -7.1 0:45
All results . . . . . . . . . . . . Yes
3.200 0.200 287.3 -1.5 -7.3 0:50
Table of measured values . . . . . . Yes
3.400 0.200 285.2 -2.1 -10.5 0:54
E - V curve . . . . . . . . . . . . Yes
3.600 0.200 282.8 -2.4 -12.0 0:59
3.800 0.200 279.7 -3.1 -15.5 1:03
4.000 0.200 275.6 -4.1 -20.3 1:08
4.200 0.200 268.8 -6.8 -34.2 1:12
4.367 0.167 257.4 -11.4 -68.0 1.18
Application note: 4.446
4.474
0.079
0.028
243.5
227.5
-13.9
-15.9
-176.5
-569.5
1.22
1:29
EQP1 4.494 0.020 190.7 -36.8 -1840.2 1:43
Cr(VI) in etching solutions 4.514 0.020 168.6 -22.2 -1108.1 1:53
4.535 0.021 160.8 -7.8 -371.3 2:01

A DP550 Phototrode with starch solution as an indica-


tor can be used instead of a DM140 electrode if the E-V curve:
solution is clear enough.
Sample preparation:
See above. In addition, 1 g NH4HF2 is added as a mask-
ing agent for Al.
(Literature: DL40 Application no. 306)

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


Instruments: METTLER TOLEDO DL55
Substance: Cr(III) as Cr2O3 METTLER TOLEDO ST20A
M = 151.99 ; z = 3 Printer EPSON LX400

Preparation: - 10 mL nitric acid 1:1 Method: 40003


- 50 mL 0.1 mol/L acid
cerium sulphate solution Accessories: Titration beakers ME-101446
- 5 min. heating, 50°C Peristaltic pump SP250
1 burette DV1020
Titrant: Sodium nitrite, NaNO2
c(1/2 NaNO2) = 0.2 mol/L Indication: DM140

Standard: For cerium sulphate (see M543):


Di-sodium oxalate, C2Na2O4
For sodium nitrite (see M544):
Sulphanilic acid, C6H7NO3S

Results:

Sample Cr2O3 content Comments

Cr bath (g/L)

n = 2

x 4.2782
srel -- DL40 Appl. no. 308

Page 50/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40003 Cr(III) as Cr2O3
Version 16/01/2001 10:10

Title
Method ID . . . . . . . . . . . . . 40003
• The method was developed on the DL40 titrator
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Cr(III) as Cr2O3
. . . 16/01/2001 10:10
(see DL40 applications No. 308) and has been
Sample
Sample ID . . . . . . . . . . . . . Cr2O3
adapted for the DL5x- and DL7x-titrators.
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
5.0
• The Cr(III) content is expressed as Cr2O3 and is
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
152
3
detemined by back titration after addition of ex-
Titration stand . . . . . . .
Pump . . . . . . . . . . .
.
.
.
.
.
.
ST20A
No
cess cerium sulphate solution.
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O
Volume . . . . . . . .
Conditioning . . . . . . .
.
.
.
.
.
.
10.0
No
Sample preparation
Temperature sensor . . . . . .
Stir
. . . Manual
1) Add 10 mL nitric acid 1:1 to 5 mL chromium bath
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
. . . 50
. . . 10
in a glass beaker.
EQP titration
Titrant/Sensor 2) 50 mL acid cerium sulphate solution c(1/2
Titrant . . . . . . . . . . . . . 1/2 NaNO2
Concentration [mol/L] . . . . . . 0.2 Ce(SO4)2 = 0.05 mol/L) are added by using the dis-
Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . mV pensing function of the titrator. This corresponds to
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.0 2.5 mmol/L equivalent Ce(IV)
Wait time [s] . . . . . . . . . . 0
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.1 3) The sample solution is heated during 5 minutes at
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
Equilibrium controlled
0.5
50°C. During this time, Cr(III) is oxidized by ex-
∆t [s] . . . . . . . . . . . . . 1.0 cess Ce (IV) to Cr(VI):
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 30.0
Recognition 3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+ (z = 3)
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No whereas Ce(IV) is reduced to Ce(III):
Tendency . . . . . . . . . . . . Negative
Termination
at maximum volume [mL] . . . . . 20.0 Ce4+ → Ce3+ + e-
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . .
comb. termination criteria
.
.
.
.
.
.
1
No
Procedure
Evaluation
Procedure . . . . . . . . . . . . Standard 1) A Ce(IV)-blank is determined using a similar meth-
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No od as for the determination of Cr(III). The blank
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 value is stored as auxiliary value H2 (mmol).
Calculation
Formula . . . . . . . . . . . . . . R=(H2-Q)*C/m 2) Cr(III) is then determined by a back-titration of ex-
Constant . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 4 cess Ce(IV) using sodium nitrite as a titrant:
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Cr2O3

2Ce4+ + NO2- + Η2Ο → 2Ce3+ + NO3- + 2Η+


Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=Q
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 2
(z =2)
Result unit . . . . . . . . . . . . mmol
Result name . . . . . . . . . . . . Cr2O3
Statistics . . . . . . . . . .
Calculation
. . . Yes
Chemicals
Formula . . . . . . . . . . . . . . R3=VEQ
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 3
• Acidic cerium sulphate solution: Either 40.43 g
Result unit . . . . . . . . . . . . mL Ce(SO4)2•4H2O or 63.26 g Ce(NH4)4(SO4)4• 2H2O
Result name . . . . . . . . . . . . Titrant cons.
Statistics . . . . . . . . . . . . . Yes are dissolved in 500 mL 1 mol/L sulphuric acid.
Report
Output . . . . . . . . . . . . . . . Printer Heat it p to 70°C in a water bath. After coling to
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes room temperature, fill the 1 L flask to th emark with
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes deionized water.
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
.
.
.
.
No
No Literature
Disposal • DL40 application no. 308, 1985
Special waste • Applications M543 and M544, in Application bro-
chure No. 18., "Standardization of Titrants", 2000.
Other titrators
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 Instruments: METTLER TOLEDO DL53


and V2O5 , 25 mL Epson matrix printer LX800
with serial inteface 8148
Substance: Cr(VI) as K2Cr2O7
(M = 294.19 ; z = 6) Method: 25001
V(V) as V2O5
(M = 181.88 ; z = 2) Accessories: Titration beakers ME-101446

Preparation: See next page (Remarks) Indication: DM140

Titrant: Fe(NH4)2(SO4)2 • 6H2O (FAS):


M = 392.14
c(FAS) = 0.1 mol/L

Standard: Potassium dichromate, K2Cr2O7


(see application M548)

Results:

K2Cr2O7 + V2O5 n srel K2Cr2O7 V2O5 n srel

Content (mmol) 0.86956 5 0.318 0.6195 0.25008 4 0.2079

Content (g) 0.3037 0.2274

Theoretical
content (g) 0.3067 0.232

Recovery rate (%) 99.020 98.01

Reactions
1) 1st FAS titration:
1.1 6 Fe2+ + Cr2O72- + 14 H+ → Fe3+ + 2 Cr3+ + 7 H2O
where
Cr2O72- + 14 H+ + 6 e- = 2 Cr3+ + 7 H2O (z = 6)

1.2 2 Fe2+ + V5+ = V3+ + 2 Fe3+ (z = 2)

2) V3+ to V5+:
5V3+ + 2MnO4- + 16Η+ = 5V5+ + 2Mn2+ + 8Η2O
3) 2nd FAS titration: see 1.2
Page 52/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 25001 Cr/V
Version 16/01/2001 15:30
• The method was developed on the DL25 titrator
Title
Method ID . . . . . . . . . . . . . 25001
(see DL25 application no. 21) and has been adapt-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Cr/V
. . . 16/01/2001 15:30
ed for the DL5x- and DL7x-titrators.
Sample
Sample ID . . . . . . . . . . . . . K2Cr2O7/V2O5
• The sample is dissolved in sulphuric acid. It oxi-
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
25.0
didized with KMnO4 to ensure that chromium and
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
294.26
6
vanadium are present in their highest oxidation
Titration stand . . . . . . . . . . Stand 1 state. The first titration with FAS gives the sum of
Temperature sensor . . . . . . . . . Manual
Stir Cr and V in mmol. Iron (Fe(II)) reduces Cr(VI) to
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 Cr(III), while vanadium(V) is reduced to V(III).
EQP titration
Titrant/Sensor In a second step , V(III) is again oxidized by KMnO4
Titrant . . . . . . . . . . . . . FAS
Concentration [mol/L] . . . . . . 0.1 to V5+ and titrated with FAS. The difference be-
Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . mV tween the first and the second FAS titration accounts
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.0 for the chromium content.
Wait time [s] . . . . . . . . . . 15
Titrant addition . . . . . . . . . . Dynamic
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
.
.
.
.
.
.
4.0
0.1 Sample preparation
∆V(min) . . . . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.2
Equilibrium controlled
1) 0.5 g of sample are heated in 30 mL 10%
∆E [mV] . . . . . . . . . . . . . 0.5 sulphuric acid until complete dissolution.
∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
2) In a 250 mL flask dilute with deionized water.
Recognition 3) Take 25 mL aliquots and add KMnO4 solution
Threshold . . . . . . . . . . . . 200
Steepest jump only . . . . . . . No dropwise (KMnO4: 5g/100mL).
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Negative 4) Add 5 mL conc. HCl to eliminate excess
Termination
at maximum volume [mL] . . . . . 20.0 KMnO4 present in the solution.
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No 5) Heat until violet permanganate colour disap-
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 pears, and cool to room temperature.
comb. termination criteria . . . No
Evaluation 6) 1st titration with FAS (V2O5 + K2Cr2O7).
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No 7) Add again KMnO4 until violet is persistent.
Potential 2 . . . . . . . .
Stop for reevaluation . . .
.
.
.
.
.
.
No
Yes
8) Excess KMnO4 is eliminated by adding KNO2
Calculation
Condition . . . . . . . . . . neq=0 solution dropwise (KNO2 = 1g/100 mL).
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R=Q 9) Add 0.5 g urea to eliminate excess KNO2.
Decimal places . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
.
.
5
mmol
10) 2nd titration with FAS (V2O5).
Result name . . . . . . . . . . . . K2Cr2O7/V2O5 11) The difference between first and second result
Statistics . . . . . . . . . . . . . Yes
Calculation gives the chromium content.
Formula . . . . . . . . . . . . . . R2=VEQ
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Titrant cons.
Chemicals
Statistics . . . . . . . . . . . . . Yes
Calculation • Fe(NH4)2(SO4)2 • 6H2O (FAS):
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . mL flask with 10% sulphuric acid and fill to the
Statistics . . . . . . . . . . . . . No
Report mark with deionized water.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes Literature
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • DL25 application no. 21, in DL25 Application
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
.
.
.
.
.
.
No
No
Brochure "Chemicals", ME-51724629 (1994).
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
.
.
.
.
.
.
No
No
• Application no. M548 and M544, in Application
∆V/∆t - t curve . . . . . . . . . . No brochure 18, "Standardization of Titrants", 2000.
• "Metallurgische Analysen", József Mika,
Budapest
Disposal • "Handbuch für das Eisenhüttenlaboratorium", 2.
Special waste Band, Chemikerausschuss des Vereins
Deutscher Eisenhüttenleute.
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77. Author: Maria José Schmid
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 53/100
METTLER TOLEDO

M188 Determination of Cr(VI) in an electroplating bath by Fe(II) titration

Sample: Cr-electroplating bath, 0.2 mL Instruments: METTLER TOLEDO DL50


Printer HP DeskJet 500
Substance: Cr(VI)
M = 99.99 ; z = 3 Method: 02

Preparation: 50 mL deionized water Accessories: Titration beakers ME-101974

Titrant: Fe(NH4)2(SO4)2 • 6H2O (FAS): Indication: DM140


M = 392.14, c(FAS) = 0.1 mol/L

Standard: Potassium dichromate, K2Cr2O7


(see application M548)

Results:

METTLER TOLEDO DL50 Titrator V2.3 Laboratorium Helio Repro BV


Kerkrade

Method 02 Chroom(VI)-bep in Cr-baden 03-11-2000 10:58


Measured 01-12-2000 13:15
User W.Jongen

ALL RESULTS

No. ID Sample size and results

1 CrHe128/11 0.2 mL
R1 = 320.31 g/L Chroomzuur
2 CrHe128/11 0.2 mL
R1 = 320.55 g/L Chroomzuur
3 CrHe128/11 0.2 mL
R1 = 320.10 g/L Chroomzuur

STATISTICS
Number results R1 n = 3
Mean value x = 320.32 g/L Chroomzuur
Standard deviation s = 0.22772 g/L Chroomzuur
Rel. standard deviation srel = 0.071 %

Page 54/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 02 Chroom(VI)-bep in Cr-baden
Version 03-11-2000 10:58

Title • Cr(VI) is reduced to Cr(III) by the addition of ti-


Method ID . . . . . . . . . . . . . 02
Title . . . . . . . . . . . . . Chroom(VI)-bep in trant: Fe(II) is oxidized to Fe(III) according to:
Cr-baden
Date/time . . . . . . . . . . . . . 03-11-2000 10:58
Sample
Sample ID . . . . . . . . . . . . . CrHe128/11 3 Fe2+ + Cr6+ = 3 Fe3+ + 2 Cr3+
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . . . . . . 0.2
Molar mass M . . . . . . . . . . . . 99.99
Equivalent number z . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Chemicals
Stir
Speed [%] . . . . . . . . . . . . . 30
Time [s] . . . . . . . . . . . . . . 15 • Fe(NH4)2(SO4)2 • 6H2O (FAS), 0.1 mol/L:
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . (NH4)2Fe(SO4)2
Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DM140
mL flask with 10% sulphuric acid and fill to the
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
.
.
.
.
.
.
mV
to volume
mark with deionized water.
Volume [mL] . . . . . . . . . . . 17
Wait time [s] . . . . . . . . . . 60
Titrant addition . . . . . . . . . . Dynamic
∆E(set) [mV] . . . . . . .
∆V(min) [mL] . . . . . . .
.
.
.
.
.
.
4.0
0.05
Literature
∆V(max) [mL] . . . . . . . . . . 0.08
Measure mode . . . . . . . . . . . . Equilibrium controlled • Application no. M548 in Application bro-
∆E [mV] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 1.0 chure18, "Standardization of Titrants", 2000.
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 20.0
Recognition
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No Table of measured values:
Tendency . . . . . . . . . . . . Negative
Volume Increment Signal Change 1st deriv. Time
Termination
at maximum volume [mL] . . . . . 25.0 mL mL mV mV mV/mL min:s
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No ET1 0.0000 979.0 0:03
after number EQPs . . . . . . . . Yes 9.7140 9.7140 973.2 -5.8 -0.6 0:26
n = . . . . . . . . . . . . . 1 14.5710 4.8570 975.1 1.9 0.4 1:09
comb. termination criteria . . . No ET2 17.0000 2.4290 984.4 9.2 3.8 2:16
Evaluation 17.0800 0.0800 984.2 -0.2 -2.4 2:19
Procedure . . . . . . . . . . . . Standard 17.1600 0.0800 984.2 0.0 0.0 2:23
Potential 1 . . . . . . . . . . . No 17.2400 0.0800 984.2 0.1 0.8 0:26
Potential 2 . . . . . . . . . . . No 17.3200 0.0800 984.5 0.3 3.2 2:30
Stop for reevaluation . . . . . . Yes 17.4000 0.0800 984.5 0.0 0.0 2:33
Calculation 17.4800 0.0800 985.1 0.6 7.3 2:36
Formula . . . . . . . . . . . . . . R=Q*C/m 17.5600 0.0800 985.1 0.1 0.8 2.40
Constant . . . . . . . . . . . . . . C=M/z 17.6400 0.0800 985.6 0.5 0.5 2:44
Decimal places . . . . . . . . . . . 2 17.7200 0.0800 986.1 0.5 6.5 2:49
Result unit . . . . . . . . . . . . g/L 17.8000 0.0800 986.2 0.1 1.6 2:53
Result name . . . . . . . . . . . . Chroomzuur 17.8800 0.0800 986.8 0.5 6.5 2:57
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . .
19.7200 0.0800 987.6 -2.5 -31.5 5:33
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 19.8000 0.0800 967.2 -20.4 -254.4 5:54
Result unit . . . . . . . . . . . . 19.8500 0.0500 960.1 -7.1 -142.2 6:14
Result name . . . . . . . . . . . . 19.9300 0.0800 866.5 -93.6 -1170.4 6:35
Statistics . . . . . . . . . . . . . No EQP1 19.9800 0.0500 596.5 -270.0 -5399.8 6:41
Calculation 20.0300 0.0500 575.8 -20.7 -413.6 7:12
Formula . . . . . . . . . . . . . . 20.0800 0.0500 564.9 -10.9 -218.4 7:15
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer+Computer
E-V curve:
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Special waste

Other titrators
DL53, DL58, DL70ES, DL77. Author: F. Saes, MT-NL/ W. Jongen
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 55/100
METTLER TOLEDO

M189 Determination of free cyanide in a copper bath

Sample: Copper bath, Instruments: METTLER TOLEDO DL53


aliquots of 1 mL from diluted Matrix printer Epson LX800
solution of 10 mL in 100 mL. with serial inteface 8148
AT261
Substance: Free cyanide, CN-
M = 26.02, z = 2 Method: 25003

Preparation: 5 mL potassium iodide, KI, 10% Accessories: Titration beakers ME-101974


40 mL deion. water
Indication: DP550 Phototrode with
Titrant: Silver nitrate, AgNO3 DIN-Lemo Adapter ME-89600
c(AgNO3) = 0.1 mol/L

Standard: Sodium chloride


(see application M525)

Results:

CN- n Comments

Mean value 26.84 g/kg 6 DL25 application note


in

Standard 0.346 g/kg DL25 Application brochure


deviation s "Petroleum products and
electroplating"
ME-51 724 627
Rel. standard 1.29 %
deviation srel

Page 56/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 25003 Free CN- in Cu bath
Version 17-01-2001 10:50 • The cyanid content determination in e.g. brass elec-
Title
Method ID . . . . . . . . . . . . . 25003
troplating bath is very important to achieve opti-
. . . Free CN- in Cu bath
Title . . . . . . . . . .
Date/time . . . . . . . . . . . . . 17-01-2001 10:50
mum plating efficiency.
Sample
Sample ID . . . . . . . . . . . . . Cu bath • The method was developed on the DL25 titrator
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . . . . . . 1.0 and has been adapted for the DL5x-/DL7x-titrators.
Molar mass M . . . . . . . . . . . . 26.01
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . .
Temperature sensor . . . . . .
.
.
.
.
.
.
Stand 1
Manual Sample preparation
Stir
Speed [%] . . . . . . . . . . . . . 50
1) 10 mL copper bath are diluted to 100 mL with
Time [s] . . . . . . . . . . .
EQP titration
. . . 10 deionized water.
Titrant/Sensor
Titrant . . . . . . . . . . . . . AgNO3
2) 1 mL aliquot is poured in the titration beaker.
Concentration [mol/L] . . . . . . 0.1 3) Add 5 mL 10% potassium iodide solution (KI).
Sensor . . . . . . . . . . . . . DP550
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
.
.
.
.
.
.
mV
to volume
4) 40 mL deionized water is added to the sample.
Volume [mL] . . . . . . . . . . . 1.5
Wait time [s] . . . . . . . . . . 20
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
.
.
.
.
.
.
Dynamic
4.0
Reaction
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
.
.
.
.
.
.
0.02
0.2
• A soluble complex Ag(CN)2 - is first formed by
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
Equilibrium controlled
0.5
the reaction between silver and cyanide ion:
∆t [s] . . . . . . . . . . . . . 1.0 Ag+ + 2 CN- = Ag(CN)2 -
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0 As long as free cyanide is still present, the solu-
Threshold . . . . . . . . . . . . 200 tion remains clear, but the first excess of silver
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No causes formation of a white solid that mark the
Tendency . . . . . . . . . . . . Negative
Termination endpoint:
at maximum volume [mL] . . . . . 20.0
at potential . . . . . . . . . . No Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes • To obtain a accurate determination of the
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No endpoint, potassium iodide is used as an indica-
Evaluation
Procedure . . . . . . . . . . . . Standard tor.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No During titration, any silver iodide which would
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 tend to form will be kept in solution by the excess
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m of cyanide ion always present until the equiva-
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
2
lence point is reached:
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
g/L
Sample content
AgI + 2 CN- = [Ag(CN)2] - + I-
Statistics . . . . . . . . . .
Calculation
. . . Yes
• After the equivalence point, the formation of yel-
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=R1*10
low silver iodide will lead to a turbidity increase
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L which indicates the end point.
Result name . . . . . . . . . . . . Bath content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=Q*C3 Chemicals
Constant . . . . . . . . . . . . . . C3=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg • 10% Potassium iodide, KI: 50 g KI and 50 g
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
CN in sample
No
NaOH are dissolved in deionized water, and di-
Report
Output . . . . . . . . . . . . . . . Printer
luted to 500 mL in a volumetric flask.
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . .
Sample data . . . . . . . . .
.
.
.
.
.
.
Yes
No
Literature
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • Application note, DL25 Application Brochure
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No "Petroleum and electroplating", ME-51724627.
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No • Vogel's textbook of quantitative inorganic analy-
∆V/∆t - t curve . . . . . . . . . . No
sis, 4th edition, Longman Group Limited , 1978.
• D.A. Skoog, D.M. West, "Fundamentals of Ana-
Disposal lytical Chemistry", Holt, Rinehart, and Winston,
Cyanide waste 1969.
• Application no. M525 in Application bro-
chure18, "Standardization of Titrants", 2000.
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77. Author: R. Böhlen, MT Switzerland
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 57/100
METTLER TOLEDO

M190 Determination of free cyanide in a cyanidic zinc bath

Sample: Cyanidic zinc bath, Instruments: METTLER TOLEDO DL53


aliquots of 1 mL Matrix printer Epson LX800
with serial inteface 8148
Substance: Free cyanide, CN- AT261
M = 26.02, z = 2
Method: 40004
Preparation: 40 mL deionized water
5 mL 20% NaOH (5 mol/L) Accessories: Titration beakers ME-101974

Titrant: Silver nitrate, AgNO3 Indication: DM141


c(AgNO3) = 0.1 mol/L

Standard: Sodium chloride


(see application M525)

Results:

CN- n Comments

Mean value 50.994 g/L 5 DL40 application no. 168

as NaCN, M=49

Rel. standard 0.37 %


deviation srel

Page 58/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40004 Free CN- in Zn bath
Version 18-01-2001 10:13
• The method was developed on the DL40 titrator
Title
Method ID . . . . . . . . . . . . . 40004
and has been adapted for the DL5x- and DL7x-ti-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Free CN- in Zn bath
. . . 18-01-2001 10:13
trators.
Sample
Sample ID . . . . . . . . . . . . . Zn bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
1.0
Sample preparation
Molar mass M . . . . . . . . . . . . 26.01 1) 1 mL zinc bath are diluted in a titration beaker
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . . . . . Stand 1 by adding 40 mL deionized water.
Temperature sensor . . . . . . . . . Manual
Stir 2) 5 mL 20% NaOH solution are added.
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . AgNO3
Reaction
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DM141
• The following equation describes the interde-
Unit of meas. . . . . . . . . . . mV pendence of the different ions in a zinc bath:
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 1.0
Wait time [s] . . . . . . . . . . 10
Titrant addition . . . . . . . . . . Dynamic Na2Zn(CN)4 + 4NaOH = Na2ZnO2 + 4NaCN + 2H2O
∆E(set) [mV] . . . . . . . . . . 8.0
∆V(min) [mL] . . . . . . . . . . 0.02
∆V(max) [mL] . . . . . . . . . . 0.2
Measure mode . . . . . . . . . . . . Equilibrium controlled If excess sodium hydroxde is added, then all
∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 1.0 cyanide is set free, and can be precipitated by
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0 silver ions Ag+ added during titration:
Recognition
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
Ag+ + 2 CN- = [Ag(CN)2] -
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
15.0
No
Note that silver forms i a first step the soluble
at slope . . . . . . . . . . . . No complex Ag(CN)2- .
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard
• The indication with the DM141 combined silver
Potential 1 . . . . . . . . . . . No electrode is superior to the traditional turbidi-
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes metric indication with potassium iodide.
Condition . . . . . . . . . . neq=0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z • The Zn content analysis is described in appl.
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L M191
Result name . . . . . . . . . . . . Bath content
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=Q*C2
C2=M*1000/z
Literature
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mg
CN in sample
• DL40 application no. 168
Statistics . . . . . . . . . .
Calculation
. . . Yes • Vogel's textbook of quantitative inorganic analy-
Formula . . . . . . . . . . . . . . sis, 4th edition, Longman Group Limited , 1978.
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 • Application no. M525 in Application bro-
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . chure18, "Standardization of Titrants", 2000.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No E-V curve (DL40 application):
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Cyanide waste

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: U. Büchi / P. Schauwecker
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 59/100
METTLER TOLEDO

M191 Back-titration of zinc in a cyanidic zinc bath

Sample: Cyanidic zinc bath, Instruments: METTLER TOLEDO DL55


aliquots of 1 mL Matrix printer Epson LX800
with serial inteface 8148
Substance: Zn2+ AT261
M = 65.37, z = 2
Method: 40005
Preparation: 50 mL deionized water
5 mL buffer solution pH 10 Accessories: Titration beakers ME-101974
5 mL 37-40% formaldehyde sol. 1 additional burette drive DV90
1 additional burette DV1005
Titrant 1: EDTA, (for ZnSO4)
c(EDTA) = 0.1 mol/L
Indication: DP550 Phototrode with
Titrant 2: Zinc sulphate, ZnSO4 DIN-Lemo adapter ME-89600
c(ZnSO4) = 0.1 mol/L 0.5 mL Erio T, 0.1% solution.

Standard: For EDTA: Zinc sulphate, ZnSO4


(see appl. M528)
For ZnSO4: EDTA
(see appl. M539)

Results:

Zn2+ n Comments

Mean value 18.428 g/L 6 DL40 application no. 175

Rel. standard 0.08 %


deviation srel

Page 60/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40005 Zn in Zn bath
Version 18-01-2001 10:30
• The method was developed on the DL40 titrator
Title
Method ID . . . . . . . . . . . . . 40005
and has been adapted for the DL5x- and DL7x-ti-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Zn in Zn bath
. . . 18-01-2001 10:30
trators.
Sample
Sample ID . . . . . . . . . . . . . Zn bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
1.0
• Adjust the DP 550 at 1000 mV in deionised water
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
65.37
1
before starting titration (100% transmission).
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual
Dispense
Titrant . . . . . . . . . . . . . . EDTA
Sample preparation
Concentration [mol/L] . . . . . . . 0.1
Volume [mL] . . . . . . . . . . . . 6.0
Stir
Speed [%] . . . . . . . . . . . . . 50
1) 1 mL zinc bath are diluted in a titration beaker
Time [s] . . . . . . . . . . .
EQP titration
. . . 20 by adding 50 mL deionized water.
Titrant/Sensor 2) 5 mL buffer solution pH 10 are added
Titrant . . . . . . . . . . . . . ZnSO4
Concentration [mol/L] . . . . . . 0.1 3) 5 mL 37-40% formaldehyde solution are added.
Sensor . . . . . . . . . . . . . DP550
Unit of meas. . . . . . . . . . . mV 4) 0.5 mL indicator solution are added before
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.5 titration.
Wait time [s] . . . . . . . . . . 10
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.02
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
Equilibrium controlled
0.2
Reaction
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0 • Zn is determined by back titration after addition
Threshold . . . . . . . . . . . . 1000 of an excess of EDTA (6 mL).
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No 1. Zn(II) ions form complexes with EDTA:
Tendency . . . . . . . . . . . . Negative
Termination
at maximum volume [mL] . . . . . 10.0
at potential . . . . . . . . . . No Zn 2+ + H2-EDTA2- = Zn-EDTA2- + 2 H+
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No 2. EDTA excess is titrated with 0.1 mol/L zinc
Evaluation
Procedure . . . . . . . . . . . . Standard sulphate solution according to the above reaction.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 3. The colour change of Erio T in alkaline medium
Calculation
Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m
will be from blue to red when EDTA is titrated
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
2
with Zn(II).
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Bath content
Statistics . . . . . . . . . .
Calculation
. . . Yes
Chemicals
Formula . . . . . . . . . . . . . . R2=R1*C2
Constant . . . . . . . . . . . . . . C2=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg • Buffer solution pH 10:
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Zn in sample
Yes
70 g ammonium chloride, NH4Cl, and 570 mL
Calculation
Formula . . . . . . . . . . . . . .
ammonium hydroxide, NH4OH, are dissolved in
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 0
1000 mL volumetric flask. Diluto to the mark
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
with deionized water.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No Literature
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes • DL40 application no. 175
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
.
.
.
.
.
.
No
Yes
• Applications no. M528 and 538 in Application
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
.
.
.
.
.
.
Yes
No
brochure18, "Standardization of Titrants", 2000.
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Zinc is precipitated as zinc hydroxide with NaOH or
Ca(OH)2 and then filtrated (precipitate: special waste).
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: U. Büchi / P. Schauwecker
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 61/100
METTLER TOLEDO

M175 Titration of gold -Au(III)- in a standard solution

Sample: Standard solution, KAu(CN)2 Instruments: METTLER TOLEDO DL53


5 mL aliquots Matrix printer Epson LX800
with serial inteface 8148
Substance: Au3+ AT261
M = 196.97, z = 1
Method: 40005
Preparation: 50 mL deionized water
Adjust to pH 3-5 with HNO3. Accessories: Titration beakers ME-101974

Titrant: Silver nitrate, AgNO3 Indication: DM141


c(AgNO3) = 0.1 mol/L

Standard: Sodium chloride


(see application M525)

Results:

Au3+ n Comments

Mean value 3.9978 g/L 5 DL40 application no. 8121

Theoretical 4.0134 g/L 1.46739 g KAu(CN)2 in 250 mL


content in 250 mL deionized water
M(KAu(CN)2) = 288.07

Rel. standard 0.07 %


deviation srel

Page 62/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40005 Au(III)
Version 18-01-2001 16:30 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . . . . . 40005
Title . . . . . . . . . . . . . Zn in Zn bath trators.
Date/time . . . . . . . . . . . . . 18-01-2001 16:30
Sample
Sample ID . . . . . . . . . . . . . Au-solution
Entry type . . . . . . . . . . . . . Fixed volume Sample preparation
Volume [mL] . . . . . . . . . . . 5.0
Molar mass M . . . . . . . . . . . . 196.97 1) 5mL standard solution are diluted in a titration
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1 beaker by adding 50 mL deionized water.
Temperature sensor . . . . . . . . . Manual
Stir 2) Adjust to pH 3-5 by carefully adding 1 mol/L
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 nitric acid (or more concentrated, if necessary).
EQP titration
Titrant/Sensor CAUTION:
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
AgNO3
0.1
If the pH is lowered below pH 3, then HCN is
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
DM141
mV
formed, which is extremely toxic! Therefore
Predispensing . . . . . . . .
Titrant addition . . . . . . .
.
.
.
.
.
.
No
Dynamic
work in a fume hood.
∆E(set) [mV] . . . . . . . . . . 8.0
∆V(min) [mL] . . . . . . . . . . 0.02
∆V(max) [mL] . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.2
Equilibrium controlled
Reaction
∆E [mV] . . . . . . . . . . . . . 0.5 • Gold is precipitated as AgAu(CN)2 during titra-
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
tion with silver nitrate:
Recognition
Threshold . . . . . . . . . . . . 800
Steepest jump only . . . . . . . No Ag + + Au(CN)2- = AgAu(CN)2
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
10.0
No
Nitric acid is added to increase the steepness of
at slope . . . . . . . . . . . . No the potential jump at the equivalence point.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation • If the standard solution should contain chloride,
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No then the latter can be determined by continuing
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes the analysis until a second equivalence point is
Condition . . . . . . . . . . neq=0
Calculation found. This is due to the precipitation of silver
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z chloride in the sample solution.
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Au content
Yes
• Gold electroplating baths contain free cyanide.
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
Interference from free cyanide can be avoided by
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 3
adjusting the pH to 5-6 using 30-40% formalde-
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Consumption
hyde solution. After a waiting time of 15-20 min-
Statistics . . . . . . . . . .
Calculation
. . . Yes utes, the titration can be started.
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
.
.
.
.
.
.
No
No Literature
∆V/∆t - t curve . . . . . . . . . . No
• DL40 application no. 8121, 1982.

• Vogel's textbook of quantitative inorganic analy-


Disposal sis, 4th edition, Longman Group Limited , 1978.
Special waste. CAUTION: cyanide is toxic!
• Application no. M525 in Application bro-
Other titrators chure18, "Standardization of Titrants", 2000.
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: MT Analytical, Application laboratory
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 63/100
METTLER TOLEDO

M176 Determination of gold by precipitation reaction with hydroquinone

Sample: Various gold alloys Instruments: - METTLER TOLEDO DL70ES/77


0.02 - 0.08 g - METTLER balance AT261
- Printer: HP Deskjet
Compound: Gold, Au
M = 196.97; z = 3 Method: - gold, test
- cer, hydr (standardization)
Preparation: Solvent mixture
conc. HCl: 5 mL / conc. HNO3: 1.5 mL Accessories: - Two burette drives DV90
HCl 0.1 mol/L: 40 mL
- Two 10 mL burettes DV910
- Glass beaker ME-101446
Titrant 1: Hydroquinone - Pump ME-65241
c(1/2 C6H6O2) = 0.05 mol/L - Ultrasonic bath

Titrant 2: Cerium(IV) sulfate Indication: - DM140-SC at Sensor 2


c(Ce(SO4)2) = 0.01 mol/L

Standard: Pure gold

Results:

Samples Weight n Results


Given carat value [g] x srel

24 0.023 - 0.024 3 23.995 0.23

18 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
Introduction Chemistry and Calculations
To determine pure gold or its content in alloys we have 1. Gold (Au) is oxidized to the Au3+ ion by aqua regia.
chosen the precipitation method with hydroquinone. 2. Au3+ is reduced by an excess of hydroquinone:
Most of the associated metals do not interfere with the Au precipitates and quinone is formed
determination. As the precipitation of gold is too slow to
OH O
execute a direct titration with hydroquinone, an excess
of hydroquinone is added to the dissolved gold. The pH ~ 1
excess is titrated back with cerium sulfate. Three individual 2 Au3+ + 3 = 2 Au + 6H+ + 3
methods are necessary for the gold determination: 6e -

• The cer method is used for the factor determination of OH O


cerium sulfate vs. hydroquinone. 3. The excess of hydroquinone is then oxidized by
• The hydr method is used for the standardization of cerium sulfate (back titration):
these two titrants with pure gold.
OH O
• The gold method is used for the determination of pure
gold or its content in alloys. pH ~ 1
If the gold content is unknown, the test method is used. +2 Ce4+ = + 2 Ce3+ + 2H+
2e-
The following points indicate that these methods are OH O
suitable for the gold determination:
• The titration of hydroquinone with cerium sulfate is
mmol C6H6O2 dispensed (excess)
reproducible (see cer method).
• It has been shown that gold solutions are very stable VDISP ∗ c(1/2 C6H6O2) ∗ t
over several days when kept at low pH in hydrochloric
acid (Ref. 1). mmol Au mmol Ce(SO4)2 titrated
• It has been shown that copper, iron, zinc, nickel, plat- 1
3 ( /3 Au3+) VEQ ∗ c(Ce(SO4)2 ∗ t
inum and palladium do not interfere (Ref. 2). We
have found that also silver does not interfere.
mmol Au =
3[VDISP ∗ c(1/2 C6H6O2) ∗ t - VEQ ∗ c(Ce(SO4)2 ∗ t]
Accuracy
The accuracy which can be obtained by these methods VDISP = dispensed hydroquinone [mL]
depends on c(1/2 C6H6O2) = hydroquinone concentration [mol/L]
- the quality of weighing.
VEQ = Ce(SO4)2 consumption back titrat. [mL]
- the care with which the gold sample is prepared and
c(Ce(SO4)2) = cerium sulfate concentration [mol/L]
dissolved.
- the amount of gold taken.
- the precision of titration. Disposal
HCl/HNO3: Neutralization with NaOH
Maintenance of the Electrode Hydroquinone: Evaporate solution, special waste.
We recommend to always clean the electrode after 6 Cerium: Precipitate with NaOH and filtrate it,
gold titrations because gold contaminates the platinum special waste.
ring by forming a thin layer: Gold: Filtrate solution, special waste.
– Place it for two minutes in aqua regia and rinse thor- Other metals: Evaporate titrated or filtrated gold
oughly with deion. H2O. solution. Classify as special waste.
(See also leaflet of the DM140-SC).
References
Titration Time of one Sample 1. A. Chow, The Stability of Gold Solutions, Talanta 18 (1971),
453-456.
Method cer hydr gold test
2. S. C. Soundar Rajan and N. Appala Raju, Titrimetic Determina-
Time [min] 6 10 10-15 20-25 tion of Gold by Precipitation with Hydroquinone, Talanta 22
(1975), 185-189.

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 65/100
METTLER TOLEDO

M177 Titer determination of cerium sulfate vs. hydroquinone

Sample: Hydroquinone solution Preparation of the Hydroquinone Solution


c(1/2 C6H6O2) = 0.05 mol/L: 1.5 mL – Dissolve 2.753 g hydroquinone in 900 mL deion.
H2O using a 1 L volumetric flask.
Compound: Hydroquinone
– Add 10 mL conc. H2SO4 and fill up to the mark with
M = 110.11; z = 2
deion. H2O.
Preparation: HCl 0.1 mol/L: 40 mL
Preparation of the Cerium(IV) Sulfate Solution
Titrant: Cerium(IV) sulfate
c(Ce(SO4)2) = 0.01 mol/L – 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 cer Factor Ce(SO4)2/C6H4(OH)2 02-April-1993 13:35


User
Measured 02-April-1993 13:38

RESULTS

No ID1 ID2 Sample amount and results

1/1 C6H6O2 1.5 mL Fixed volume U


R1 = 0.98115 Factor
1/2 C6H6O2 1.5 mL Fixed volume U
R1 = 0.98202 Factor
1/3 C6H6O2 1.5 mL Fixed volume U
R1 = 0.98217 Factor
1/4 C6H6O2 1.5 mL Fixed volume U
R1 = 0.98261 Factor

STATISTICS
Number results R1 n = 4
Mean value x = 0.98199 Factor
Standard deviation s = 0.000611 Factor
Rel. standard deviation srel = 0.062 %
Outlier test: no outliers!

AUXILIARY VALUE
New value H2 = 0.981989 Factor

Page 66/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method "cer" Remarks
Method cer Factor Ce(SO4)2/C6H4(OH)2
Version 02-April-1993 13:35 • The cerium sulfate solution is unstable because a
Title precipitation occurs. We recommend to prepare a
Method ID . . . . . . . . . . . . . cer
Title . . . . . . . . . . . . . . . Factor Ce(SO4)2/C6H4(OH)2 new solution every 2 days.
Date/time . . . . . . . . . . . . . 02-April-1993 13:35
Sample
Number samples . . . . . . . . . . . 4
• The hydroquinone solution is stable but we
Titration stand . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Stand 1
Fixed volume U
recommend to prepare a new solution every 10
Volume [mL] . . . . . . . .
ID1 . . . . . . . . . . . . .
.
.
.
.
.
.
1.5 mL
C6H6O2
days.
Molar mass M . . . . . . . . . . . . 110.11
Equivalent number z . . . . . . . . 2
Temperature sensor . . . . . .
Pump
. . . Manual
Calculation
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
Volume [mL] . . . . . . . . . . . . 40.0 • Fixed volume U of hydroquinone =
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2 dispensed volume VDISP = 1.5 mL
Concentration . . . . . . . . . . . 0.05
Volume [mL] . . . . . . . . . . . . 1.5
Stir
Speed [%] . . . . . . . . . . . . . 50 VDISP * c(1/2 C6H6O2)
Time [s] . . . . . . . . . . .
Titration
. . . 10
fce/hy =
Titrant . . . . . . . . . . .
Concentration [mol/L] . . . .
.
.
.
.
.
.
Ce(SO4)2
0.01
VEQ * c(Ce(SO4)2)
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predespensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 6.3 • If the mean value ❘ of fce/hy is less than 0.9 or greater
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0 than 1.1, the INSTRUCTION function is displayed.
Limits ∆V . . . . . . . . . . Absolute
∆V (min) [mL] . . . . . . . 0.01
∆V (max) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU • The mean value ❘ of fce/hy is stored as auxiliary value
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 2.0 H2. It is used to calculate the titer of cerium sulfate
t(min) [s] . . . . . . .
t(max) [s] . . . . . . .
.
.
.
.
.
.
3.0
30.0 versus gold (see method "hydr").
Threshold . . . . . . . . . . . . 2000.0
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs .
n = . . . . . . . . . .
.
.
.
.
.
.
Yes
1 Table of measured values
Evaluation procedure . . . . . . Standard
Calculation Volume Increment Signal Change 1st deriv. Time
Result name . . . . . . . . . . . . Factor mL mL mV mV mV/mL min:s
Formula . . . . . . . . . . . . . . R=VDISP*0.05/(VEQ*c)
ET1 0.0000 432.8 0:30
Constant . . . . . . . . . . . . . .
3.6000 3.6000 455.0 22.2 6.2 0:57
Result unit . . . . . . . . . . . .
5.4000 1.8000 468.6 13.6 7.5 1:16
Decimal places . . . . . . . . . . . 5 ET2 6.3000 0.9000 479.6 11.1 12.3 1:31
Statistics 6.5000 0.2000 482.2 3.1 15.4 1:40
Ri (i=index) . . . . . . . . . . . . R1 6.7000 0.2000 486.7 4.0 20.2 1:49
Standard deviation s . . . . . . . . Yes 6.9000 0.2000 491.3 4.6 23.1 2:04
Rel. standard deviation srel . . . . Yes 7.1000 0.2000 498.1 6.8 33.9 2:19
Outlier test . . . . . . . . . . . . Yes 7.2780 0.1780 507.0 8.9 49.9 2:37
Instruction 7.3990 0.1210 517.1 10.1 83.3 2:54
At least one solution is bad! 7.4670 0.0680 525.1 8.1 118.4 3:10
Please renew! 7.5190 0.0520 534.6 9.5 181.7 3:27
Condition . . . . . . . . . . . . . Yes 7.5510 0.0320 542.5 7.9 247.2 3:44
Condition . . . . . . . . . . . . (x<0.9)?(x>1.1) 7.5760 0.0250 551.7 9.2 366.8 4:07
Auxiliary value 7.5920 0.0160 561.0 9.4 586.2 4:24
ID text . . . . . . . . . . . . . . Factor 7.6020 0.0100 567.9 6.9 686.0 4:41
Formula . . . . . . . . . . . . . . H2=x 7.6120 0.0100 578.7 10.9 1085.0 4:58
Record 7.6220 0.0100 595.1 16.3 1630.9 5:18
Output unit . . . . . . . . . . . . Printer EQP1 7.6320 0.0100 640.9 45.8 4585.0 5:39
All results . . . . . . . . . . . . Yes 7.6420 0.0100 681.5 40.6 4059.8 5:53
Table of values . . . . . . . . . . Yes 7.6520 0.0100 708.5 27.0 2702.0 6:13
E - V curve . . . . . . . . . . . . Yes

E-V curve

Authors: MT Analytical, Application laboratory


Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 67/100
METTLER TOLEDO

M178 Standardization of hydroquinone with pure gold

Sample: Pure gold: 0.023 - 0.026 g Instruments: - METTLER TOLEDO DL70ES/77


- METTLER balance AT261
Compound: Gold - Printer: HP Deskjet
M = 196.97; z = 3
Method: hydr
Preparation: Solvent mixture
conc. HCl: 5 mL / conc. HNO3: 1.5 mL Accessories: - Two burette drives DV90
HCl 0.1 mol/L: 40 mL - Two 10 mL burettes DV910
- Glass beaker ME-101446
Titrant 1: Hydroquinone - Pump ME-65241
c(1/2 C6H6O2) = 0.05 mol/L - Ultrasonic bath

Titrant 2: Cerium(IV) sulfate Indication: - DM140-SC at Sensor 2


c(Ce(SO4)2) = 0.01 mol/L

Results:

Method hydr Titer of C6H6O2, Ce(SO4)2 06-April-1993 13:39


User
Measured 07-April-1993 13:03
RESULTS
No ID1 ID2 Sample amount and results
1/1 Gold 0.024295 g Weight m
R1 = 4.778 mL
R2 = 0.22028 mmol C6H6O2
R3 = 0.99996 Titer C6H6O2
1/2 Gold 0.023605 g Weight m
R1 = 4.842 mL
R2 = 0.21503 mmol C6H6O2
R3 = 0.99924 Titer C6H6O2
1/3 Gold 0.023662 g Weight m
R1 = 4.835 mL
R2 = 0.21545 mmol C6H6O2
R3 = 0.99788 Titer C6H6O2
1/4 Gold 0.02332 g Weight m
R1 = 4.867 mL
R2 = 0.21285 mmol C6H6O2
R3 = 0.99784 Titer C6H6O2
STATISTICS
Number results R3 n = 4
Mean value x = 0.99873 Titer C6H6O2
Standard deviation s = 0.001046 Titer C6H6O2
Rel. standard deviation srel = 0.105 %
Outlier test: no outliers!
TITER
Titrant 1/2 C6H6O2 0.05 mol/L
New titer t = 0.998729
TITER
Titrant Ce(SO4)2 0.01 mol/L
New titer 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
Sample Preparation
Title
Method ID . . . . . . . . . . . . . hydr A careful sample preparation is mandatory for reprodu-
Title . . . . . . . . . . .
Date/time . . . . . . . . .
. . . . Titer of C6H6O2, Ce(SO4)2
. . . . 06-April-1993 13:39
cible results.
Sample – Weigh in a gold sample of approx. 0.025 g.
Number samples . . . . . . . . . . . 4
Titration stand . . . . . . . . . . Stand 1 – Clean it with ethanol and let it dry - use tweezers.
Entry type . . . . . . . . .
Lower limit [g] . . . . .
.
.
.
.
.
.
.
.
Weight m
0.023
– Weigh in this sample with a precision of 0.001 mg
Upper limit [g] . . . . . . . . . 0.026 and put it in the glass beaker.
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . . . . . . 196.967 – Add 5 mL conc. HCl and 1.5 mL conc. HNO3 (fume
Equivalent number z . . . . . . . . 3
Temperature sensor . . . . . . . . . Manual hood). Never use prepared aqua regia, it is unstable!
Pump
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
– To dissolve the gold place the beaker on a heating
Volume [mL] . . . . . . . . . . . . 40.0 plate (110 to 130 °C).
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2 The dissolution time can be reduced by using an
Concentration . . . . . . .
Volume [mL] . . . . . . . .
. . . . 0.05
. . . . 1.4*H2+304.6*m
ultra-sonic bath (room temperature).
Stir – Evaporate to almost dryness (color changes from
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 180 yellow to orange), but never evaporate to complete
Calculation
Result name . . . . . . . . . . . . dryness! This would cause the reduction of gold and
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=VDISP*5/H2-C
C=m*1523*H2
give false results!
Result unit . . . . . . . . . . . . mL – Rinse the beaker walls with 5 mL conc. HCl and eva-
Decimal places . . . . . . . . . . . 3
Titration porate again to eliminate the nitrous compounds.
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
.
.
Ce(SO4)2
0.01
– Repeat this procedure until no yellow fumes are
Sensor . . . . . . . . . . . . . . . DM140-SC formed anymore.
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP – Let the sample cool to room temperature, then titrate.
Predespensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 0.9*R
Titrant addition . . . .
∆E(set) [mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0
Table of measured values
Limits ∆V . . . . . . . . . . Absolute Volume Increment Signal Change 1st deriv. Time
∆V (min) [mL] . . . . . . . 0.01 mL mL mV mV mV/mL min:s
∆V (max) [mL] . . . . . . . 0.2
ET1 0.0000 449.7 0:03
Measure mode . . . . . . . . . . EQU 2.5020 2.5020 457.5 7.8 3.1 0:13
∆E [mV] . . . . . . . . . . . 0.5 3.7530 1.2510 462.6 5.0 4.0 0:21
∆t [s] . . . . . . . . . . . . 2.0 ET2 4.3800 0.6270 465.8 3.3 5.2 0:27
t(min) [s] . . . . . . . . . . 3.0 4.5800 0.2000 467.1 1.3 6.3 0:32
t(max) [s] . . . . . . . . . . 30.0 4.7800 0.2000 468.4 1.3 6.7 0:37
4.9800 0.2000 469.8 1.4 7.0 0:42
Threshold . . . . . . . . . . . . 1000.0
5.1800 0.2000 471.4 1.6 8.1 0:47
EQP range . . . . . . . . . . . . Yes 5.3800 0.2000 473.1 1.7 8.4 0:53
Limit A . . . . . . . . . . . 500 5.5800 0.2000 475.2 2.1 10.5 0:58
Limit B . . . . . . . . . . . 800 5.7800 0.2000 477.4 2.2 10.9 1:04
Maximum volume [mL] . . . . . . . 10.0 5.9800 0.2000 480.1 2.7 13.7 1:09
Termination after n EQPs . . . . Yes 6.1800 0.2000 483.6 3.4 17.2 1:15
6.3800 0.2000 488.1 4.6 22.8 1:22
n = . . . . . . . . . . . . . 1
6.5800 0.2000 495.2 7.1 35.3 1:28
Evaluation procedure . . . . . . Standard 6.7460 0.1660 506.4 11.2 67.5 1:37
Calculation 6.8260 0.0800 520.1 13.7 171.5 1:46
Result name . . . . . . . . . . . . C6H6O2 6.8550 0.0290 530.0 9.9 340.3 1:54
Formula . . . . . . . . . . . . . . R2=VDISP*0.05 6.8700 0.0150 539.9 9.9 662.6 2:03
Constant . . . . . . . . . . . . . . 6.8800 0.0100 548.6 8.7 868.0 2:15
6.8900 0.0100 558.8 10.2 1022.0 2.30
Result unit . . . . . . . . . . . . mmol
6.9000 0.0100 571.0 12.3 1225.0 2:46
Decimal places . . . . . . . . . . . 5 6.9100 0.0100 589.5 18.4 1840.9 3:07
Calculation 6.9200 0.0100 625.8 36.3 3633.0 3:38
Result name . . . . . . . . . . . . Titer C6H6O2 EQP1 6.9300 0.0100 679.2 53.4 5340.8 4:08
Formula . . . . . . . . . . . . . . R3=C3/(R2-VEQ*c*H2) 6.9400 0.0100 703.3 23.1 2408.0 4:30
Constant . . . . . . . . . . . . . . C3=(m*1000*z)/M 6.9500 0.0100 712.1 8.8 882.0 4:40
Result unit . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 5
Statistics E-V curve
Ri (i=index) . . . . . . . . . . . . 3
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
Titer
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Concentration [mol/L] . . . . . . . 0.05
Formula t = . . . . . . . x
Titer
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Concentration [mol/L] . . . . . . . 0.01
Formula t = . . . . . . . x*H2
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Table of values . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Auxiliary value Disposal
ID text . . . . . . . . . . . . . . Titer of C6H6O2
Formula . . . . . . . . . . . . . . H3=x Special waste.

Authors: MT Analytical, Application laboratory


Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 69/100
Other titrators
DL70ES, DL77.
Remarks
d. Titer determination of Ce(SO4)2 vs. gold
Calculations
The factor fce/hy was obtained by the standardization of
a. Dispensing of hydroquinone cerium sulfate with hydroquinone (method "cer").
An excess of hydroquinone is dispensed depending The titer of cerium sulfate must be referred to gold.
on the size of the gold sample. Furthermore, approx.
7 mL of the cerium sulfate titrant should be consumed tce = thy * fce/hy = thy * H2
by the back titration. Thus the dispensed volume of
hydro-quinone (VDISP) is calculated in the DISPEN-
SE function.
mL hydroquinone mL hydroquinone where
VDISP = reacted with gold+ back titrated with
Ce(SO4)2 VDISP = dispensed volume of hydroquinone
[mL]
z * m * 1000 7 mL * c(Ce(SO4)2) * fce/hy
1
+ VEQ = cerium sulfate consumption by back
VDISP = M * c( /2 C6H6O2) c(1/2 C6H6O2)
titration
= 304.6 * m + 1.4 * H2
VEQth = calculated cerium sulfate consumption
for back titration
z= equivalent number of gold = 3
The best accuracy is achieved if the consumption of m= size of gold sample [g]
hydroquinone and cerium sulfate is less than 1 M= molar mass of gold = 196.967
burette volume each, i.e. 10 mL. Therefore the c(1/2 C6H6O2)= hydroquinone concentration =
sample weight must lie in the range of 0.023 and
0.026 g gold. Also the titer values of both titrants 0.05 mol/L
must lie in the range of 0.95 and 1.1. c(Ce(SO4)2 = cerium sulfate concentration =
0.01 mol/L
b. Predispensing of cerium sulfate (back titration) fce/hy = factor of cerium sulfate vs. hydroquinone
Predispensing is always applied to speed up the (stored as H2)
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.
Reaction Time
VDISP c(1/2 C6H6O2) z * m * 1000 The complete reduction of gold with hydroquinone takes
VEQth = * –
c(Ce(SO4)2) M * c(Ce(SO4)2) * fce/hy about 2 minutes; thus the stirring time shall not be less
fce/hy
than 180 s.
VEQth = VDISP/H2 * 5 – m * 1523 * H2

c. Titer determination of C6H6O2 vs. gold

thy = z * m * 1000
1
M (VDISP * c( /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.

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 Determination of the gold content in alloy

Sample: Various gold alloys with a known Instruments: - METTLER TOLEDO DL70ES/77
(±10%) gold content - METTLER balance AT261
0.02 - 0.08 g - Printer: HP Deskjet

Compound: Gold, Au Method: - gold


M = 196.97; z = 3 - cer, hydr (standardization)

Preparation: Solvent mixture Accessories: - Two burette drives DV90


conc. HCl: 5 mL / conc. HNO3: 1.5 mL - Two 10 mL burettes DV910
HCl 0.1 mol/L: 40 mL - Glass beaker ME-101446
- Pump ME-65241
Titrant 1: Hydroquinone - Ultrasonic bath
c(1/2 C6H6O2) = 0.05 mol/L
Indication: - DM140-SC at Sensor 2
Titrant 2: Cerium(IV) sulfate
c(Ce(SO4)2) = 0.01 mol/L

Standard: Pure gold (Mxxx), and Mxxx

Method gold Purity of gold samples 08-April-1993 8:48


User
Measured 08-April-1993 15:36

RESULTS

No ID1 ID2 Sample amount and results


1/1 Gold 0.024295 g Weight m
R1 = 38.044 % purity
R2 = 9.131 carat purity
1/2 Gold 0.023605 g Weight m
R1 = 38.070 % purity
R2 = 9.137 carat purity
1/3 Gold 0.023662 g Weight m
R1 = 38.108 % purity
R2 = 9.146 carat purity
1/4 Gold 0.02332 g Weight m
R1 = 38.010 % purity
R2 = 9.123 carat purity

STATISTICS
Number results R1 n = 4
Mean value x = 38.058 % purity
Standard deviation s = 0.041247 % purity
Rel. standard deviation srel = 0.108 %
Outlier test: no outliers!

STATISTICS
Number results R2 n = 4
Mean value x = 9.134 carat purity
Standard deviation s = 0.009899 carat purity
Rel. standard deviation srel = 0.108 %
Outlier test: no outliers!

AUXILIARY VALUE
New VALUE H4 = 0.375

Page 72/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method "gold" Remarks
Method gold Purity of gold samples • Before executing this method the carat or percent
Version 08-April-1993 8:48
value of the alloy has to be entered as auxiliary value
Title
Method ID . . . . . . . . . . . . . gold
H1. If the gold content is unknown, use the "test"
Title . . . . . . . . . . . . . . . Purity of gold samples method (see M180). Enter thy as H3.
Date/time . . . . . . . . . . . . . 08-April-1993 8:48
Sample • The gold concentration of the sample entered as
Number samples . . . . . . . . . . . 4
Titration stand . . . . . . . . . . Stand 1 carat or percent is automatically transformed into the
Entry type . . . . . . . . .
Lower limit [g] . . . . .
.
.
.
.
.
.
.
.
Weight m
0.02
fraction of gold and stored as H4 using the AUXILIARY
Upper limit [g] . . . . . . . . . 0.08 VALUE functions.
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . . . . . . 196.967
Equivalent number z . . . . . . . . 3 Sample Preparation
Temperature sensor . . . . . . . . . Manual
Auxiliary value
ID text . . . . . . . . . . . . . .
Proceed with the sample preparation as described in
Formula . . . . . . . . . . . . . . H4=H1/24 method "hydr". The following remarks are important:
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . H1<=24 • Press alloys as thin as possible using a rolling device
Auxiliary value
ID text . . . . . . . . . . . . . . so that the dissolution is easier.
Formula . . . . . . . . . . . . . . H4=H1/100
Condition . . . . . . . . . . . . . Yes • Use an ultrasonic bath especially for silver alloys, be-
Condition . . . . . . . . . . . . (H1>24)!(H1<=100)
Pump cause silver chloride does passivate the gold surface.
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
Volume [mL] . . . . . . . . . . . . 40.0 • Evaporate the aqua regia solution.
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2 • Add 5 mL conc. HCl to the beaker and put it in the
Concentration . . . . . . . . . . . 0.05
Volume [mL] . . . . . . . . . . . . 1.2*H2+304.6*m*H4/H3
ultrasonic bath for 5 minutes.
Stir
Speed [%] . . . . . . . . . . . . . 50 • Evaporate again.
Time [s] . . . . . . . . . . . . . . 180
Titration • If the alloy is not yet dissolved, repeat the procedure.
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Concentration [mol/L] . . . . . . . 0.01 • Never evaporate to complete dryness!
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . .
Predespensing 1 . . . . .
.
.
.
.
.
.
.
.
EQP
mL
Sample Weight (g)
Volume [mL] . . . . . . . . . 2.1
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0
Content (carat) lower limit upper limit
Limits ∆V . . . . . . . . . . Absolute
∆V (min) [mL] . . . . . . . 0.02
24 0.023 0.026
∆V (max) [mL] . . . . . . . 0.2 21 0.026 0.030
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 18 0.031 0.034
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 14 0.040 0.044
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 400.0 12 0.046 0.052
EQP range . . . . . . . . . . . . Yes
Limit A . . . . . . . . . . . 500 9 0.062 0.069
Limit B . . . . . . . . . . . 700
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 Dispensing of Hydroquinone
Evaluation procedure . . . . . . Standard
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
purity
R=100*(QDISP-Q)*C
• An excess of hydroquinone is dispensed depending
Constant . . . . . . . . . . . . . . C=M/(m*z*1000) on the sample size and the gold concentration.
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 3 • Furthermore, the dispensed volume (VDISP) is
Calculation
Result name . . . . . . . . . . . . purity
calculated for a consumption of 6 mL cerium sulfate
Formula . . . . . . . . . . . . . . R2=24*(QDISP-Q)*C2 during the back titration. VDISP is determined and
Constant . . . . . . . . . . . . . . C2=M/(m*z*1000)
Result unit . . . . . . . . . . . . carat dispensed by the DISPENSE function.
Decimal places . . . . . . . . . . . 3
Statistics
Ri (i=index) . . . . . . . . . . . . R1
VDISP =
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes
= mL hydroquinone + mL hydroquinone back
Statistics reacted with gold titrated with Ce(SO4)2
Ri (i=index) . . . . . . . . . . . . R2
Standard deviation s . . . . . . . . Yes
Rel. standard deviation srel . . . . Yes z * m * Aux * 1000 6 mL * c(Ce(SO4)2) * fce/hy
Outlier test . . . . . . . . . . . . Yes = 1
+
Record M * c( /2 C6H6O2) * thy c(1/2 C6H6O2)
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
= 304.6 * m * H4/H3 + 1.2 * H2

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 73/100
Calculation of the result Reaction Time
• The complete reduction of gold with hydroquinone
takes about 3 minutes; thus the stirring time shall not
The gold content Au is:
be less than 180 s.

Au = 24 * M * (QDISP – Q) [carat] Titration Parameters


z * 1000 * m • 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
where we recommend to increase the minimum increment
VDISP = dispensed volume of hydroquinone ∆V(min) to >0.02 mL.
[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
c(1/2 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 H4)

Disposal
Special waste.

Other titrators
DL70ES, DL77. Authors: MT Analytical, Application laboratory
Page 74/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
METTLER TOLEDO

M180 Determination of the approximate gold content content in alloys

Sample: Various gold alloys with an unknown gold Remarks


content: 0.03 - 0.06 g With this method the gold content can be determined
within approx. 3%. The gold method can then be
Method "test" executed to obtain the precise result.
Method test Approximate gold content
Version 10-April-1993 11:09 1st TITRATION function: The gold reduction with hydroqui-
Title
Method ID . . . . . . . . . . . . . test
none is done by a titration in order
Title . . . . . . . . . . .
Date/time . . . . . . . . .
. . . . Approximate gold content
. . . . 10-April-1993 11:09
• to determine the total amount of C6H6O2 dispensed
Sample
Number samples . . . . . . . . . . . 1 and
Titration stand . . . . . .
Entry type . . . . . . . . .
.
.
.
.
.
.
.
.
Stand 1
Weight m • to obtain an excess of at least 1 mL C6H6O2 (titrant
Lower limit [g] . . . . .
Upper limit [g] . . . . .
.
.
.
.
.
.
.
.
0.03
0.06 addi-tion ∆V = 0.5 mL).
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . . . . . . 196.967
Equivalent number z . . . . . . . . 3 Titration Curve: Gold Reduction with Hydroquinone
Temperature sensor . . . . . . . . . Manual
Pump
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
Volume [mL] . . . . . . . . . . . . 40.0
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
Titration
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Concentration [mol/L] . . . . . . . 0.05
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Titrant addition . . . . . . . . INC
∆V [mL] . . . . . . . . . . . 0.5
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 10.0
t(max) [s] . . . . . . . . . . 40.0
Threshold . . . . . . . . . . . . 200.0
EQP range . . . . . . . . . . . . Yes
Limit A . . . . . . . . . . . 800
Limit B . . . . . . . . . . . 500
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1 The total amount of C6H6O2 dispensed is stored as
Evaluation procedure . . . . . . Standard
Auxiliary value auxiliary value H5.
ID text . . . . . . . . . . . . . . Amount of C6H6O2
Formula . . . . . . . . . . . . . . H5=Q+QEX
Stir 2nd TITRATION function: The excess of hydroquinone is
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 120 titrated back with cerium sulfate.
Titration
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Concentration [mol/L] . . . . . . . 0.01
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . .
Titration mode . . . . . . .
.
.
.
.
.
.
.
.
mV
EQP
Titration Curve: Back Titration with Cerium Sulfate
Titrant addition . . . . . . . . DYN
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Absolute
∆V (min) [mL] . . . . . . . 0.02
∆V (max) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 400.0
EQP range . . . . . . . . . . . . Yes
Limit A . . . . . . . . . . . 500
Limit B . . . . . . . . . . . 700
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard
Calculation
Result name . . . . . . . . . . . . content
Formula . . . . . . . . . . . . . . R=100*(H5-Q[2])*C
Constant . . . . . . . . . . . . . . C=M/(m*z*1000)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 1
Calculation
Result name . . . . . . . . . . . . content
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R2=24*(H5-Q[2])*C2
C2=M/(m*z*1000)
Disposal
Result unit . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
carat
1
Special waste.
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes
Authors: MT Analytical, Application laboratory
Electronics and electroplating applications 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%) Instruments: METTLER TOLEDO DL53
0.5 - 1 g Matrix printer Epson LX800
with serial inteface 8148
Substance: Lead, Pb4+ as lead oxide, PbO2 AT261
M = 239.2, z = 2
Method: 40006
Preparation: 30% HNO3 , 15 mL
10% H2O2 , 5 mL Accessories: Glass titration beakers
Hot deioniezd water, 30 mL. ME-101446

Titrant: Potassium permanganate, KMnO4 Indication: DM140


c(1/5 KMnO4) = 0.1 mol/L

Standard: Di-sodium oxalate, Na2C2O4


(see application M527)
Results:

PbO2 n Comments

Mean value 8.5547 % 5 DL40 application no. 305

Theoretical 8-10 % Sample size: 1 g


content
Consumption: 20 mL
Rel. standard 0.33 %
deviation srel

Mean value 32.64 % 5 DL40 application no. 305

Theoretical 30 ± 3 % Sample size : 0.5 g


content

Rel. standard 0.48 % Consumption: 12 mL


deviation srel

Mean value 2.84 mmol 4 DL40 application no. 305

Theoretical 0 Blank value


content
Consumption: 27.5 mL

Rel. standard 0.48 %


deviation srel

Page 76/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40006 PbO2
Version 19-01-2001 17:32 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-
Method ID . . . . . . . . . . . . . 40006
Title . . . . . . . . . . . . . PbO2 titrators.
Date/time . . . . . . . . . . . . . 19-01-2001 17:32
Sample • The Pb(IV) content is expressed as PbO2 and is
Sample ID . . . . . . . . . . . . . Lead in batteries
Entry type . . . . . . . . . . . . . Weight detemined by back titration after addition of ex-
Lower limit [g] . . . . . . . . . 0.5
Upper limit [g] . . . . . . . . . 1.5 cess hydrogen peroxide solution.
Molar mass M . . . . . . . . . . . . 239.2
Equivalent number z . . . . . . . . 2
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual Sample preparation
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
EQP titration 1) Dissolve the sample in a glass titration beaker by
Titrant/Sensor
Titrant . . . . . . . . . . . . . 1/5 KMnO4 adding 15 mL of 30% nitric acid HNO3. Stir the
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DM140 solution until all red traces are dissolved.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No 2) 5 mL 10% hydrogen peroxide solution are added
Titrant addition . . . . . . .
∆E(set) [mV] . . . . . . .
.
.
.
.
.
.
Dynamic
8.0
by using the dispensing function of the titrator.
∆V(min) [mL] . . . . . . .
∆V(max) [mL] . . . . . . .
.
.
.
.
.
.
0.02
0.2
Pb(IV) is reduced to Pb(II) by H2O2:
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 2.0
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
.
.
.
.
.
.
1.0
5.0
Pb4+ + H2O2 = Pb2+ + O2 + 2 H+ (z = 2)
t(max) [s] . . . . . . . . . . . 30.0
Recognition
Threshold . . . . . . . . . . . . 300 Pb4+ + 2 e- = Pb2+
Steepest jump only . . . . . . . No
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive
Termination 3) 30 mL hot deionized water are added and stir to
at maximum volume [mL] . . . . . 30.0
at potential . . . . . . . . . . No achieve complete solvation.
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard Procedure
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes 1) The exact concentration of the H2O2-solution is de-
Condition . . . . . . . . . . neq=0
Calculation termined by performing a blank titration using a
Formula . . . . . . . . . . . . . . R=(H4-Q)*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) similar method as for the sample determination. The
Decimal places . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
.
.
4
%
blank value is stored as auxiliary value H4 (mmol).
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Pb content
Yes
2) Pb(IV) is then determined by a back-titration of
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
excess H2O2 using potassium permanganate as a
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
. 3
titrant:
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption
Statistics . . . . . . . . . .
Calculation
. . . Yes 2MnO4 - + 5 Η2Ο2 + 6 H+ = 2Mn2+ + 5O2 + 8Η2O
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . (z =2)
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No
Literature
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No • DL40 application no. 305
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • Application no. M527 in Application bro-
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No chure18, "Standardization of Titrants", 2000.
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Special waste.

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: MT Analytical, Application laboratory
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 77/100
METTLER TOLEDO

M193 Complexometric titration of lead in alloy

Sample: Lead-tin-antimony alloy, Instruments: METTLER TOLEDO DL53


10 mL aliquots Rondo 60 sample changer
Olivetti ArtJet 20
Substance: Lead, Pb2+
M = 207.2, z = 1 Method: 40007

Preparation: 50 mL deion. water Accessories: Glass titration beakers


ME-101446
Titrant: EDTA
c(EDTA) = 0.1 mol/L Indication: DP550 Phototrode with
DIN-Lemo adapter ME-89600
Standard: Zinc sulphate, ZnSO4
(see application M528)

Results:

Pb2+ n Comments

Mean value 45.49 % 5 DL40 application no. 406

Consumption: 1.7 mL
Rel. standard 0.34 %
deviation srel

Mean value 98.13 % 5 DL40 application no. 403

Test with Pb((NO3)2 standard


Preparation:
Rel. standard 0.21 % 1. use buffer solution pH 5.4
deviation srel 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 Remarks
Method 40007 Pb2+
Version 22-01-2001 10:47 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-
Method ID . . . . . . . . . . . . . 40007
Title . . . . . . . . . . . . . Pb2+ titrators.
Date/time . . . . . . . . . . . . . 22-01-2001 10:47
Sample • The Pb(II) content is detemined by complexomet-
Sample ID . . . . . . . . . . . . . Pb/Sn/Sb alloy
Entry type . . . . . . . . . . . . . Fixed volume ric titration with EDTA.
Volume [mL] . . . . . . . . . . . 10.0
Molar mass M . . . . . . . . . . . . 207.2
Equivalent number z . . . . . . . . 1
Titration stand . . . .
Pump . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
ST20A
No
Sample preparation
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H2O
Volume . . . . . . . . . . . 20.0 1) Dissolve 1-1.5 g of the finely pulverized alloy in a
Conditioning . . . . . . . . . . No
Temperature sensor . . . . . . . . . Manual 250 mL beaker.
Stir
Speed [%] . . . . . . . . . . . . . 50 2) Add 20 mL 1:1 HCl and heat
Time [s] . . . . . . . . . . . . . . 10
EQP titration 3) To the hot solution add 10 mL of 1.1 HNO3, heat
Titrant/Sensor
Titrant . . . . . . . . . . . . . EDTA until dissolution is complete.
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DP550 4) Add 20 mL of 4% KCl, 50 mL of 1.1 HCl, 50 mL
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No deion. water and 20 mL 20% tartaric acid solution.
Titrant addition . . . .
∆V [mL] . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
Incremental
0.05
5) Boil 2 minutes.
Measure mode . . . . . . . . . . . . Equilibrium controlled
6) Cool to room temperature.
∆E [mV] . . . . . . . . . . . . . 0.5 7) Add 5 drops of 0.2% aqueous solution of xylenol
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
orange and 30% hexamethylene tetramine until the
Recognition solution turns red (for this sample size you need
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . . . . . No about 35 mL).
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Positive 8) Dilute to 200 mL with 1:1 HCl.
Termination
at maximum volume [mL] . . . . . 5.0 9) Take aliquots of 10 mL.
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1 Procedure
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . . . . . Standard 1) This procedure is only suitable for the determina-
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No tion of Pb in Pb/Sn/Sb alloy. The alloy is dissolved
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 due to the formation in a strong acid medium of a
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m soluble chloro-plumbate complex.
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/(10*z)
2
2) The solution is diluted to volume using 1:1 HCl
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
%
Pb content
since no precipitate is formed at high concentra-
Statistics . . . . . . . . . .
Calculation
. . . Yes tion of HCl.
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=VEQ 3) Sn and Sb are masked by tartaric acid. Pb can be
Decimal places . . . . . . . . . . . 3 directly determined by titration with EDTA:
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . .
Pb2+ + H2-EDTA2- = Pb-EDTA2- + 2 H+
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 The colour change at the equivalence point turns
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . from red to yellow.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes Literature
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes • DL40 application no. 406
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . .
V - t curve . . . . . . . . .
.
.
.
.
.
.
No
No
• Application no. M528 in Application bro-
∆V/∆t - t curve . . . . . . . . . . No chure18, "Standardization of Titrants", 2000.
Disposal
Special waste.

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: MT Analytical, Application laboratory
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 79/100
METTLER TOLEDO

M194 Determination of nickel in an electroplating bath

Sample: Nickel bath, 0.5 mL Instruments: METTLER TOLEDO DL70


METTLER TOLEDO ST20A
Substance: Nickel as NiSO4, METTLER TOLEDO AT261
M = 262.7 g/mol, z = 1 Matrix Printer Epson LX800
with serial interface 8148
Preparation: Deionised water, 50 mL
Buffer pH 10, 10 mL Method: vd01
0.5 g Murexide/NaCl 1:200
trituration. Accessories: Titration beakers ME-101974
2 peristaltic pumps ME-65241
Titrant: EDTA, c(EDTA) = 0.1 mol/L
Indication: DP550 Phototrode at sensor 2
Standard: Zinc sulfate, c(ZnSO4) = 0.1 mol/L with DIN-Lemo adapter
(See METTLER method M007) ME-89600

Results: vd01 Nickel in Galvanic Bath measured 19-Dec-1989 15:50


19-Dec-1989 15:22 Titrator Mettler Tiel
SW Version 1.2 User J.v.d.Ouweland

RESULTS

No Identification Volume Results

1/1 0.5 mL 82.35 g/L NiSO4.6H2O


1/2 0.5 mL 82.59 g/L NiSO4.6H2O
1/3 0.5 mL 82.38 g/L NiSO4.6H2O
1/4 0.5 mL 82.07 g/L NiSO4.6H2O
1/5 0.5 mL 82.14 g/L NiSO4.6H2O
1/6 0.5 mL 82.75 g/L NiSO4.6H2O
1/7 0.5 mL 82.48 g/L NiSO4.6H2O
1/8 0.5 mL 82.31 g/L NiSO4.6H2O

STATISTICS
Number results R1 n = 8
Mean value x = 82.39 g/L NiSO4.6H2O
Standard deviation s = 0.225 g/L NiSO4.6H2O
Rel. standard deviation srel = 0.273 %

Page 80/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method vd01 Nickel in Galvanic Bath
Version 13-Sep-1991 15:22 • The Ni(II) content is detemined by complexomet-
Title ric titration with EDTA. Murexide is used as indi-
Method ID . . . . . . . . . . . . . vd01
Title . . . . . . . . . . . . . Nickel in Galvanic Bath
cator, and the colour change is monitored by a
Date/time . . . . . . . . .
Sample
. . . . 13-Sep-1991 15:22 DP550 phototrode.
Number samples . . . . . . . . . . 8
Titration stand . . . . . . . . . . ST20
Entry type . . . . . . . . . . . . . Fixed volume U
Volume [mL] . . . . . . . . . . . 0.5 Sample preparation
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
. 262.7
1) Add the mureide indicator to the sample
Equivalent number z . . . .
Pump
. . . . 1 2) The addition of water and buffer is performed au-
Auxiliary reagent . . . . . . . . . H2O tomatically by two peristaltic pumps.
Volume [mL] . . . . . . . . . . . . 10.0
Pump
Auxiliary reagent . . . . . . . . . Buffer 10
Volume [mL] . . . . . . . .
Stir
. . . . 10.0 Procedure
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 • Nickel ions forms a yellow complex with murex-
Titration
Titrant . . . . . . . . . . . . . . EDTA ide in alkaline solution:
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
.
.
.
.
.
.
.
.
DP550
As installed
Ni 2+ + Murexide - → Ni-Murexid+
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . mL Ni forms a more stable complex with EDTA:
Volume [mL] . . . . . . . . . 0.5
Titrant addition . . . .
∆E(set)[mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0 Ni-Murexid+ + EDTA 4- → Ni-EDTA2-+ Murexide-
Limits ∆V . . . . . . . . . . Absolute
∆V(min) . . . . . . . . . . 0.02 At the equivalence point, Ni(II) has been
∆V(max) . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . EQU complexed by EDTA and murexide is free in the
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 1.0 alkaline solution. There is a colour change from
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 yellow to blue-violet.
Threshold . . . . . . . . . . . 10.0
Maximum volume [mL] . . .
Termination after n EQPs
.
.
.
.
.
.
.
.
15.0
Yes
• The shape of the titration curve is somewhat af-
n = . . . . . . . . .
Evaluation procedure . .
.
.
.
.
.
.
.
.
1
Standard
fected by the concentration of the indicator. The
Calculation results, however, do not differ significantly.
Result name . . . . . . . . . . . . NiSO4.6H2O
Formula . . . . . . . . . . . . . . R=Q*C/U
Constant . . . . . . . . . . . . . . C=M/z Chemicals
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Rinse
• Buffer solution pH 10: 570 mL 25% NH3 and 70 g
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
. . . . H2O
. . . . 10.0
NH4Cl diluted with deionized water in a 1 L flask.
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
. . . . R1
. . . . Yes
Table of mesured values and E-V curve
Rel. standard deviation srel . . . . Yes
Record
Short-form method . . . . . . . . . Yes
All results . . . . . . . . . . . . Yes
Table of measured values . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes

Literature
1. METTLER TOLEDO DL70 Applications Bro-
chure No. 1
2. METTLER TOLEDO DL40 Application No. 403
3. METTLER TOLEDO Application No. M066,
M528.

Disposal
Nickel solutions: special waste

Other titrators
DL50 Graphix, DL53/55 (use standard methods)
DL58, DL77. Author: J. v.d. Ouweland, MT-NL
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 81/100
METTLER TOLEDO

M195 Determination of silver in silver alloy

Sample: Silver, silver alloys Instruments: METTLER TOLEDO DL70


approx. 0.04 g METTLER TOLEDO microbalance MT5
Printer: EPSON FX800
Compound: Silver, Ag
M = 107.868; z = 1 Method: Ag02

Preparation: Deion. H2O, 50 mL Accessories: Glass titration beaker ME-101446


HNO3 33%, 3 mL
Indication: DM141-SC at Sensor 2
Titrant: Sodium chloride
c(NaCl) = 0.1 mol/L

Standard: Silver nitrate, AgNO3


(see application M536)

Results:

AgO2 Purity of AgNO3 measured 23-04-1990 11:53


23-04-1990 10:51 Titrator
SW Version 1.2 User rvr

RESULTS

No Identification Weight Results

1/1 Ag Alloy 0.051274 g 94.9658 % Silver


1/2 Ag Alloy 0.051274 g 94.9658 % Silver
1/3 Ag Alloy 0.051274 g 94.9658 % Silver
1/4 Ag Alloy 0.051274 g 94.9658 % Silver
1/5 Ag Alloy 0.051274 g 94.9658 % Silver

STATISTICS
Number results R1 n = 5
Mean value x = 94.9922 % Silver
Standard deviation s = 0.01715 % Silver
Rel. standard deviation srel = 0.018 %
Outlier test: no outliers!

Page 82/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method AgO2 Purity of AgNO3 Sample Preparation
Version 23-04-1990 10:51
– Clean the sample with acetone and let it dry – use
Title
Method ID . . . . . . . . . . . . . AgO2 tweezers.
Title . . . . . . . . . . .
Date/time . . . . . . . . .
. . . . Purity of AgNO3
. . . . 23-04-1990 10:51
– Weigh in a sample corresponding to approx. 40 mg
Sample Ag and read to ±0.01 mg; then put it in the beaker.
– Add 3 mL of 33% HNO3 and warm up to 60 °C in a
Number samples . . . . . . . . . . . 3
Titration stand . . . . . . . . . . Stand 1
Entry type . . . . . . . . . . . . . Weight m
Lower limit [g] . . . . . . . . . 0.03
wa-ter bath until the sample is completely dissolved.
Upper limit [g] . . . . . . . . . 0.07 – Let the sample cool down to room temperature and
ID1 . . . . . . . . . . . . . . . . Ag Alloy
Molar mass M . . . . . . . . . . . . 107.868 add 50 mL deion. H2O.
Equivalent number z . . . . . . . . 1
Stir This procedure is prerequisite to achieve high precision.
Speed [%] . . . . . . . . . . . . . 60
Time [s] . . . . . . . . . . . . . . 5
Titration
Titrant . . . . . . . . . . . . . . NaCl
High Precision
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DM-141-SC
Method and preparation are designed for highest preci-
Unit of meas. . . . . . . . . . . . mV sion, i.e. RSD better than 0.050%. Our example shows
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . % nominal content a reproducibility of 0.018% RSD. This high precision is
Metered amount [%] . . . . . . 95.0
Nominal content [%] . . . . . 95.0 required, for example, by mint companies or electronic
Conversion const. . .
Titrant addition . . . .
.
.
.
.
.
.
.
.
M/(10*z)
INC
circuitry manufacturers.
∆V [mL] . . . . . . . . . . . 0.05
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 High Speed
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 The method was also streamlined to fast titrations. The
t(max) [s] . . . . . . . . . . 15.0
Threshold . . . . . . . . . . . . 500.0 titration for one sample takes only approx. 70 seconds.
Maximum volume [mL] . . . . . . . 10.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard
Calculation Table of measured values
Result name . . . . . . . . . . . . Silver
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) Volume Increment Signal Change 1st deriv. Time
Result unit . . . . . . . . . . . . % mL mL mV mV mV/mL min:s
Decimal places . . . . . . . . . . . 4
Record E1 0.000 215.9 0:03
2.223 2.223 197.4 -18.5 -8.3 0:13
Raw results . . . . . . . . . . . . Yes
3.335 1.112 175.0 -22.4 -20.2 0:21
Table of measured values . . . . . . Yes
E2 3.891 0.556 140.5 -34.5 -62.0 0:29
E - V curve . . . . . . . . . . . . Yes 3.941 0.050 134.7 -5.8 -115.6 0:34
Statistics 3.991 0.050 126.5 -8.2 -163.5 0:40
Ri (i 0 index) . . . . . . . . . . . R1 4.041 0.050 111.0 -15.5 -309.7 0:46
Standard deviation s . . . . . . . . Yes 4.091 0.050 75.6 -35.5 -709.2 0:53
Rel. standard deviation srel . . . . Yes EQP1 4.141 0.050 31.0 -44.6 -891.8 0:59
Outlier test . . . . . . . . . . . . Yes 4.191 0.050 15.0 -16.0 -319.5 1:04
Record 4.241 0.050 5.4 -9.6 -192.1 1:10
All results . . . . . . . . . . . . Yes

E-V curve

Literature

3. METTLER TOLEDO Application No. M536


(appl. brochure no. 18).

Disposal
Silver precipitate can be separated. The filtrated solu-
tion is neutralized with NaOH.

Other titrators
DL50 Graphix, DL53/55 (use standard methods)
DL58, DL77. Author: Ruth von Rotz, Application laboratory MT Analytical
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 83/100
METTLER TOLEDO

M196 Determination of free potassium cyanide in a silver bath

Sample: Copper bath, 1 mL Instruments: METTLER TOLEDO DL67


METTLER TOLEDO ST20A
Substance: Free cyanide, CN- Matrix printer Epson LX800
M = 26.02, z = 2 with serial inteface 8148
AT261
Preparation: 50 mL deion. water
Method: BL20
Titrant: Silver nitrate, AgNO3
c(AgNO3) = 0.1 mol/L Accessories: Titration beakers ME-101974
Peristaltic pump SP40
Standard: Sodium chloride
(see application M525) Indication: DM141-SC

Results:

Method BL20 KCN im cy.Ag.Bad 17-02-1994 10:46


User
Measured 24-02-1994 14:49

RESULTS

No ID1 ID2 Sample amount and results

1/1 1.0 mL Fixed volume U


R1 = 110.34 g/L KCN
R2 = 8.49 mL Verbrauch
1/2 1.0 mL Fixed volume U
R1 = 111.64 g/L KCN
R2 = 8.59 mL Verbrauch
1/3 1.0 mL Fixed volume U
R1 = 114.09 g/L KCN
R2 = 8.78 mL Verbrauch

STATISTICS
Number results R1 n = 3
Mean value x = 112.02 g/L KCN

Page 84/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method BL20 KCN im cy.Ag.Bad
Version 17-02-1994 10:46 Sample preparation
Title
Method ID . . . . . . . . . . . . . BL20
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . KCN im cy.Ag.Bad
. . . . 17-02-1994 10:46
1) 1 mL silver bath is diluted with 50 mL deion-
Sample ized water
Sample no. . . . . . . . . . . . . . 20
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
.
.
.
.
.
.
.
.
1.0 Reaction
Molar mass M . . . . . . . . . . . . 65.12
Equivalent number z . . . . . . . . 2
Temperature sensor . . . . .
Stir
. . . . Manual
• A soluble complex Ag(CN)2 - is first formed by
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
the reaction between silver and cyanide ion:
EQP titration
Titrant . . . . . . . . . . . . . . AgNO3
Concentration [mol/L] . . .
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DM141-SC
Ag+ + 2 CN- = Ag(CN)2 -
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . . . . . . to volume As long as free cyanide is still present, the solu-
Volume [mL] . . . . . . . . . 1
Titrant addition . . . . . . . . DYN tion remains clear, but the first excess of silver
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Absolute causes formation of a white solid that mark the
∆V(min) [mL] . . . . . . . 0.05
∆V(max) [mL] . . . . . . . 0.5 endpoint:
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0 Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 50.0
Maximum volume [mL] . . . . . . . 30.0
Termination after n EQPs . . . . Yes
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . KCN E-V curve
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Verbrauch
Statistics . . . . . . . . . . . . . Yes
Statistik
Ri (i=Index) . . . . . . . . . . . . R1
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes

Literature
• Application note, DL25 Application Brochure
"Petroleum and electroplating", ME-51724627.
• Vogel's textbook of quantitative inorganic analy-
sis, 4th edition, Longman Group Limited , 1978.
• D.A. Skoog, D.M. West, "Fundamentals of Ana-
lytical Chemistry", Holt, Rinehart, and Winston,
Disposal 1969.
Cyanide waste • Application no. M525 in Application bro-
chure18, "Standardization of Titrants", 2000.
Other titrators
DL50 Graphix, DL53/DL55/DL58, DL70ES, DL77. Author: Application laboratory, MT Germany
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 85/100
METTLER TOLEDO

M197 Titration of Tin(II) in acidic tin bath

Sample: Acidic tin bath, 2 mL Instruments: METTLER TOLEDO DL67


METTLER TOLEDO ST20A
Substance: Tin(II), Sn2+ Matrix printer Epson LX800
M = 118.71, z = 2 with serial inteface 8148
AT261
Preparation: 50 mL deion. water
Method: BL70
Titrant: Iodine, I2
c(1/2 I2) = 0.1 mol/L Accessories: Titration beakers ME-101974
Peristaltic pump SP40
Standard: Arsenic trioxide, As2O3
(see application M016) Indication: DM140-SC

Results:

Method BL70 Sn-(II) im sauren Sn-Bad 21-02-1994 16:09


User
Measured 21-02-1994 16:18

RESULTS

No ID1 ID2 Sample amount and results

1/1 2.0 mL Fixed volume U


R1 = 21.34 g/L
1/2 2.0 mL Fixed volume U
R1 = 17.79 g/L
1/3 2.0 mL Fixed volume U
R1 = 17.59 g/L

STATISTICS
Number results R1 n = 3
Mean value x = 18.91 g/L

Page 86/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method BL70 Sn-(II) im sauren Sn-Bad
Version 21-02-1994 16:09 Sample preparation
Title
Method ID . . . . . . . . . . . . . BL70
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . KCN im cy.Ag.Bad
. . . . 21-02-1994 16:09
1) 2 mL acidic silver bath is diluted with 50 mL
Sample
Sample no. . . . . . . . . . . . . . 20
deionized water.
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
.
.
.
.
.
.
.
.
2.0
Reaction
Molar mass M . . . . . . . . . . . . 118.71
Equivalent number z . . . . . . . . 2
Temperature sensor . . . . .
Stir
. . . . Manual
• Stannous tin Sn(II) is converted quantitatively
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
into stannic tin Sn(IV) by titration with iodine
EQP titration
Titrant . . . . . . . . . . . . . . 1/2 I2
in the presence of hydrochloric acid:
Concentration [mol/L] . . . . . . . 0.1
Sensor . . . . . . . . . . . . . . . DM140-SC
Unit of meas. . . . . . . .
Titration mode . . . . . . .
.
.
.
.
.
.
.
.
mV
EQP
SnCl2 + 2HCl + I2 = SnCl4 + 2 HI
Predispensing 1 . . . . . . . . . to volume
Volume [mL] . . . . . . . . . 0
Titrant addition . . . . . . . . DYN where
∆E(set) [mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Relative
∆V(min) [%dosVol] . . . . . 0.5
∆V(max) [%buVol] . . . . . 5.0 Sn2+ = Sn4+ + 2 e-
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 I2 + 2 e- = 2 I-
∆t [s] . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 2.0
t(max) [s] . . . . . .
Threshold . . . . . . . .
.
.
.
.
.
.
.
.
20.0
100.0
• Sn(II) is oxidized to Sn(IV) by iodine, and iodine
Maximum volume [mL] . . .
Termination after n EQPs
.
.
.
.
.
.
.
.
50.0
Yes
is reduced to iodide.
n = . . . . . . . . .
Evaluation procedure . .
.
.
.
.
.
.
.
.
1
Standard
• Hydrochloric acid must be present in order to sup-
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
ply chloride ions for the oxidation, otherwise the
Constant . . . . . . . . . .
Decimal places . . . . . . .
.
.
.
.
.
.
.
.
C=M/z
2
readily hydrolysed Sn(SO4)2 is produced. If nec-
Result unit . . . . . . . . . . . . g/L essary, add 5 mL concentrated HCl.
Result name . . . . . . . . . . . . Sn2+
Statistics . . . . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 10.0
Statistik
Ri (i=Index) . . . . . . . . . . . . R1
Record
Output unit . . . . . . . . . . . . Printer
All results . . . . . . . . . . . . Yes

Application note

• 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 Literature


Na2S2O3 (see application M526).
• Application note, MT Germany, in application
brochure "Galvanik", 1995.
Disposal • K.E. Langford, J.E. Parker, "Analysis of electro-
CAUTION: arsenic trioxide is very poisonous! plating and related solutions", 4th edition, Robert
Special waste Draper Ltd. , 1971.
• Application no. M016, Application brochure 9,
Other titrators "Standardization of Titrants II" ME-51724652,
DL50 Graphix 1994.
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 Instruments: METTLER TOLEDO DL53


Matrix printer Epson LX800
Substance: Zn2+ , M = 161.4, z = 1 with serial inteface 8148
ZnSO4 , M = 65.37, z = 1 AT261

Method: 40008
Preparation: 10 mL deionized water
50 mL buffer pH 4.5 Accessories: Titration beakers ME-101974
30 mg Xylenol orange
Indication: DP550 Phototrode with
Titrant: EDTA, DIN-Lemo adapter ME-89600
c(EDTA) = 0.1 mol/L 30 mg Xylenol orange.

Standard: Zinc sulphate, ZnSO4


(see appl. M528)

Results:

Results n Comments

Mean value ZnSO4: 5 DL40 application no. 84-22


7.9824 g/L

SO42- :
4.7875 g/L

Rel. standard 0.39 %


deviation srel

Page 88/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40008 ZnSO4 in spin-bath
Version 24-01-2001 11:15
• The method was developed on the DL40 titrator
Title
Method ID . . . . . . . . . . . . . 40008
and has been adapted for the DL5x- and DL7x-ti-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . ZnSO4 in spin-bath
. . . 24-01-2001 11:15
trators.
Sample
Sample ID . . . . . . . . . . . . . Spin bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
5.0
• Adjust the DP 550 at 1000 mV in deionised water
Molar mass M . . . . . . . . .
Equivalent number z . . . . .
.
.
.
.
.
.
161.4
1
before starting titration (100% transmission).
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual
Stir
Speed [%] . . . . . . . . . . . . . 50
Sample preparation
Time [s] . . . . . . . . . . . . . . 15
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . EDTA
1) 5 mL spin bath are diluted in a titration beaker
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DP550
by adding 10 mL deionized water.
Unit of meas. . . . . . . . . . . mV 2) 50 mL buffer solution pH 4.5 are added
Predispensing . . . . . . . . . . . No
Titrant addition . . . . . . . . . . Incremental 3) 30 mg Xylenol orange are added to the sample
∆V [mL] . . . . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . . . Equilibrium controlled solution.
∆E [mV] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0 Reaction
Threshold . . . . . . . . . . . . 200
Steepest jump only . . . . . . . No
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Positive
• Zinc ions form a red complex with xylenol orange
Termination
at maximum volume [mL] . . . . . 20.0
in acidic solution:
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No Zn2+ + Xylenol 2- → Zn-Xylenol
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No By adding EDTA during titration, Zn forms a more
Evaluation
Procedure . . . . . . . . . . . . Standard stable complex with EDTA:
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . .
Stop for reevaluation . . .
.
.
.
.
.
.
No
Yes
Zn-Xylenol + EDTA 4- → Zn-EDTA + Xylenol 2-
Condition . . . . . . . . . . neq=0
Calculation At the equivalence point, all Zn ions have been
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/z complexed by EDTA and xylenol orange is free in
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . g/L the acidic solution. There is a colour change from
Result name . . . . . . . . . . . . ZnSO4 Bath cont.
Statistics . . . . . . . . . . . . . Yes red to yellow.
Calculation
Formula . . . . . . . . . . . . . . R2=Q*C2/m
Constant . . . . . . . . . . . . . . C2=96.01/z
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . g/L Chemicals
Result name . . . . . . . . . . . . SO42- in sample
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ • Buffer solution pH 4.5:
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 4 60 mL glacial acetic acid and 50 g sodium
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption acetateare dissolved in a 1 L volumetric flask.
Statistics . . . . . . . . . . . . . No
Report Dilute to the mark with deionized water.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No Literature
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes • DL40 application note no. 84-22
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No • Applications no. M528 in Application bro-
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No chure18, "Standardization of Titrants", 2000.
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Zinc is precipitated as zinc hydroxide with NaOH or
Ca(OH)2 and then filtrated (precipitate: special waste).

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratoy MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 89/100
METTLER TOLEDO

M199 Determination of sulphate in a spin bath by precipitation titration

Sample: Diluted spin-bath, (1:100) Instruments: METTLER TOLEDO DL53


Aliquot 1 mL Matrix printer Epson LX800
with serial inteface 8148
Substance: SO42- , M = 96.01, z = 1 AT261

Preparation: 20 mL deionized water Method: 40009


30 mL acetone
1 mL mixed indicator Accessories: Titration beakers ME-101974

Titrant: Barium perchlorate, Ba(ClO4)2 Indication: DP550 Phototrode with


c(Ba(ClO4)2) = 0.005 mol/L DIN-Lemo adapter ME-89600
1 mL mixed indicator.
Standard: EDTA
(see appl. M540)

Results:

Results n Comments

Mean value SO42- : 5 DL40 application no. 84-222


332.78 g/L

Rel. standard 0.20 %


deviation srel

Mean value SO42- : 7 DL40 application no. 106


2.9766 g/L The brine contained 300 g/L
i.e. more than 100 times the
molar sulphate concentration
Rel. standard 0.26 % Standardization:
deviation srel 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
Method Remarks
2-
Method 40009 SO4 in spin-bath
Version 24-01-2001 16:30 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . . . . . 40009
Title . . . . . . . . . . . . . SO42- in spin-bath
trators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Spin bath
Fixed volume
• Adjust the DP 550 at 1000 mV in deionised water
Volume [mL] . . . . . . . .
Molar mass M . . . . . . . . .
.
.
.
.
.
.
1.0
96.01
before starting titration (100% transmission).
Equivalent number z . . . . . . . . 1
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . .
Stir
. . . Manual
Sample preparation
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 30
EQP titration
Titrant/Sensor
1) 1 mL spin bath are diluted in a 100 mL volumetric
Titrant . . . . . . . . . .
Concentration [mol/L] . . .
.
.
.
.
.
.
Ba(ClO4)2
0.005
flask by adding deionized water.
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
DP550
mV
2) 1 mL aliquot is taken and added to the titration bea-
Predispensing . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Yes
3.0
ker.
Wait [s] . . . . . . . . . . . . 20 3) 20 mL deionized water are added.
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.1 4) Add 30 mL acetone.
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 2.0 Steps 3+4: The aqueous mixture is prepared in ad-
∆t [s] . . . . . . . . . . . . . 10.0
t(min) [s] . . . . . . . . . . . 10.0 vance and degassed in an ultrasonic bath before
t(max) [s] . . . . . . . . . . . 45.0
Recognition use. 50 mL are then added to the sample.
Threshold . . . . . . . . . . . . 100
Steepest jump only . . . . . . . No 5) If necessary, acidify the sample to pH 3-6 with
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . . . . . Negative aqueous perchloric acid 0.05 mol/L.
Termination
at maximum volume [mL] . . . . . 20.0
6) 1 mL mixed indicator is added to the sample prior
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No titration.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation Reaction
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes • Sulphate SO42- is determined by precipitation titra-
Condition . . . . . . . . . . neq=0
Calculation tion with barium perchlorate:
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
2
SO42- + Ba2+ → BaSO4
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
SO42- sample
Yes
• For a better recognition of the endpoint an indica-
Calculation tor is added to the sample solution.
Formula . . . . . . . . . . . . . . R2=Q*100
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . SO42- bath Chemicals
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ
Constant . . . . . . . . . . . . . . • Mixed indicator:
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mL In a 50 mL volumetric flask 0.12 mL 1.6% meth-
Result name . . . . . . . . . . . . Consumption
Statistics . . . . . . . . . . . . . No ylene blue solution and 50 mg Thorin are dis-
Report
Output . . . . . . . . . . . . . . . Printer solved in 5 mL 0.1 mol/L hydrochloric acid. Fill
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes up to the mark with deionized water.
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
.
.
.
.
.
.
Yes
Yes
Literature
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No • DL40 application note no. 84-22
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No • DL40 application no. 106
∆V/∆t - t curve . . . . . . . . . . No
• Applications no. M528 in Application bro-
chure18, "Standardization of Titrants", 2000.
Disposal
Special waste).

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratoy MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 91/100
METTLER TOLEDO

M200 Titration of fluoride in soldering salts

Sample: Soldering salts, 1 g Instruments: METTLER TOLEDO DL53


Matrix printer Epson LX800
Substance: F - , M = 18.998, z = 3 with serial inteface 8148
AT261
Preparation: 150 mL deionized water
heat at 50°C, 10 minutes Method: 40010
10 mL buffer pH 6
Accessories: 250 mL titration beakers
Titrant: Lanthanum nitrate, La(NO3)3 ME-23829
c( 1/3 La(NO3)3 ) = 0.1 mol/L
Indication: DX219 Fluoride ISE
Standard: Sodium fluoride, NaF DX200 Reference electrode
(Bridge electrolyte:
1 mol/L KNO3)

Results:

Results n Comments

Mean value F- : 4 DL40 application note


2.17 % no. 8317

Rel. standard 0.20 %


deviation srel

Page 92/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
-
Method 40010 F soldering salts
Version 24-01-2001 16:30 • The method was developed on the DL40 titrator
Title and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . . . . . 40010
Title . . . . . . . . . . . . . F- soldering salts trators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
Soldering salts
Weight Sample preparation
Lower limit [g] . . . . . . . . . 0.8
Upper limit [g] . . . . . . . . . 1.2
Molar mass M . . . . . . . . . . . . 18.998
Equivalent number z . . . . . . . . 3 1) Approx. 1 g soldering salts are dissolved in 150 mL
Titration stand . . . . . . .
Temperature sensor . . . . . .
.
.
.
.
.
.
Stand 1
Manual
deionized water .
Stir
Speed [%] . . . . . . . . . . . . . 50
2) The sample solution is heated at 50°C under stir-
Time [s] . . . . . . . . . . .
EQP titration
. . . 30 ring during 10 minutes.
Titrant/Sensor
Titrant . . . . . . . . . . . . . La(NO3)3
3) After cooling to room temperature, 10 mL buffer
Concentration [mol/L] . . .
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DX219
pH 6 are added before titration.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No
Titrant addition . . . . . . .
∆V [mL] . . . . . . . . . .
.
.
.
.
.
.
Incremental
0.2
Reaction
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . . 5.0 • Fluoride is precipitated by lanthanum in a slightly
t(max) [s] . . . . . . . .
Recognition
. . . 45.0
acid solution:
Threshold . . . . . . . . . . . . 200
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
3 F- + La3+ = LaF3
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . . . . . 20.0
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No Chemicals
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation • Buffer pH 6 solution:
Procedure . . . . . . . . . . . . Standard
Potential 1 . . . . . . . . . . . No Dissolve approx. 85 g sodium acetate in 1 L deion-
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes ized water. While monitoring the pH value, slowly
Condition . . . . . . . . . . neq=0
Calculation add glacial acetic acid to achieve pH 6.
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M/(10*z) • Titrant solution :
Decimal places . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
.
.
2
%
Dissolve 14.44 g La(NO3)3 • 6H2O in a 1 L volu-
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
% F-
Yes
metric flask and fill up to the mark to obtain the
Calculation
Formula . . . . . . . . . . . . . . R2=Q*C2
concentration c( 1/3 La(NO3)3 ) = 0.1 mol/L.
Constant . . . . . . . . . . . . . . C2=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg
Result name . . . . . . . . . . . . F- sample Literature
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ • DL40 application note no. 8317
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 4 • DL40 application no. 102.
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption
• Jander, Jahr, "Massanalyse", elaborated by
Statistics . . . . . . . . . .
Report
. . . No
Gerhard Schulze and Jürgen Simon, 14th edition,
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No
Walter de Gruyter, Berlin New York, 1986.
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Special waste.

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratory MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 93/100
METTLER TOLEDO

M201 Standardization of 1/2 Pb(NO3)2

Sample: NaF 0.1 mol/L standard solution, Instruments: METTLER TOLEDO DL53
2.5 mL Matrix printer Epson LX800
with serial inteface 8148
Substance: F - , M = 18.998, z = 2 AT261

Preparation: 20 mL deionized water Method: 40011


20 mL ispropanol
10 mL buffer pH 6 Accessories: Titration beaker ME-101974

Titrant: Lead nitrate, Pb(NO3)2 Indication: DX219 Fluoride ISE


c( 1/2 Pb(NO3)2 ) = 0.1 mol/L DX200 Reference electrode
(Bridge electrolyte:
Standard: -- 1 mol/L KNO3)

Results:

Results n Comments

Mean value Titer : 6 DL40 application no. 102


0.97892

Rel. standard 0.22 %


deviation srel

Page 94/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Method Remarks
Method 40011
Version
Titer Pb(NO3)2
26-01-2001 10:12
• The method was developed on the DL40 titrator
Title
and has been adapted for the DL5x- and DL7x-ti-
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . 40011
. . . Titer Pb(NO3)2
trators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
NaF 0.1 M
Fixed volume
Sample preparation
Volume [mL] . . . . . . . . . . . 2.5
Molar mass M . . . . . . . . . . . . 18.998
Equivalent number z . . . . . . . . 2 1) The standard solution is prepared by dissolving
Titration stand . . . . . . . . . . Stand 1
Temperature sensor . . . . . . . . . Manual 4.200 g NaF in a 1 L volumetric flask and filling up
Stir
Speed [%] . . . . . . . . . . . . . 50 to 1 L with deionized water.
Time [s] . . . . . . . . . . . . . . 30
EQP titration The fluoride solution is kept in polyethylene
Titrant/Sensor
Titrant . . . . . . . . . . . . . 1/2Pb(NO3)2 bottles.
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DX219 2) 5 mL of the standard solution are diluted with 20
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . Yes mL deionized water, 20 mL isopropanol and 5 mL
Volume [mL] . . . . . . . . . . . 4.5
Wait [s] . . . . . . . . . . . . 30 0.5 mol/L NaCl.
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.1
Measure mode . . . . . . . . . . . . Equilibrium controlled
∆E [mV] . . . . . . . . . . . . . 0.5 Reaction
∆t [s] . . . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . . . . . 45.0
Recognition • Fluoride is precipitated by lead according to:
Threshold . . . . . . . . . . . . 300
Steepest jump only . . . .
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No 2 F- + Pb2+ = PbF2
Tendency . . . . . . . . . . . . Positive
Termination
at maximum volume [mL] . . . . . 20.0
• This method can be used for the titration of sul-
at potential . . . . . . .
at slope . . . . . . . . .
.
.
.
.
.
.
No
No
phate ions.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
.
.
.
.
.
.
Standard
No
Chemicals
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes
Condition . . . . . . . . . . neq=0 • Titrant solution :
Calculation
Formula . . . . . . . . . . . . . . R=m/(VEQ*c*C) Dissolve 16.56 g Pb(NO3)2 in a 1 L volumetric
Constant . . . . . . . . . . . . . . C=1/(0.1*z)
Decimal places . . . . . . . . . . . 5 flask and fill up to the mark to obtain the concentra-
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Titer tion c( 1/2 Pb(NO3)2 ) = 0.1 mol/L
Statistics . . . . . . . . . . . . . Yes
Titer
Titrant . . . . . . . . . . . . . . 1/2Pb(NO3)2
Concentration . . . . . . . . . . . 0.1 Literature
Formula t . . . . . . . . . . . . x
Report
Output . . . . . . . . . . . . . . . Printer • DL40 application no. 102.
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes • C.E. Efstathion, T.P. Hadjhoannon,
Raw results . . . . . . . . .
Table of measured values . . .
.
.
.
.
.
.
No
Yes
Anal. Chim. Acta 109 (1979), p. 319.
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No

Disposal
Special waste.

Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. Authors: Application laboratory MT-ANA
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 95/100
Literature

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 Edi-


tion, Robert Draper Ltd, Teddington (UK), 1971 (ISBN 0-8521-8033-0).

3) Peter Wolfram Wild, "Modern Analysis for Electroplating", Hampton Hill Finishing Publica-
tions, 1974.
Peter Wolfram Wild, "Moderne Analyse für die Galvanotechnik", Eugen G. Leuze Verlag,
Saulgau (Württemberg), Germany , 1972. (Geman)

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 meth-
ods, instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot
accept any responsibility for the use or consequences of the applications contained in this brochure.
When chemicals and solvents are used, the general safety rules and the directions of the producer must be
observed.

Page 98/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
Mettler-Toledo GmbH
Analytical
CH-8603 Schwerzenbach, Schweiz
Telefon (01) 806 77 11, Fax (01) 806 73 50
Internet: http://www.mt.com

AT Mettler-Toledo GmbH., A-1100 Wien


Tel. +43-1-604 19 80, Fax +43-1-604 28 80
AU Mettler-Toledo Ltd., Port Melbourne, Victoria 3207
Tel. +61-3-9644 5700, Fax +61-3-9645 3935
BE N.V. Mettler-Toledo S.A., B-1932 Zaventem
Tel. +32-2-334 02 11, Fax +32-2-334 03 34
CH Mettler-Toledo (Schweiz) AG, CH-8606 Greifensee
Tel. +41-1-944 45 45, Fax +41-1-944 45 10
CN Mettler-Toledo (Shanghai) Ltd., Shanghai 200233
Tel. +86-21-6485 0435, Fax +86-21-6485 3351
CZ Mettler-Toledo, spol, s.r.o., CZ-12000 Praha 2
Tel. +420-2-25 49 62, Fax +420-2-2424 7583
DE Mettler-Toledo GmbH, D-35353 Giessen
Tel. +49-6-41 50 70, Fax +49-6-41 507 128
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Tel. +45-4327 0800, Fax +45-4327 0828
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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
HR Mettler-Toledo, d.o.o., HR-10000 Zagreb
Tel. +385-1-230 41 47, Fax +385-1-233 63 17
HU Mettler-Toledo, KFT, H-1173 Budapest
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
MX Mettler-Toledo S.A. de C.V., México C.P. 06430
Tel. +52-5-547 57 00, Fax +52-5-541 22 28
NL Mettler-Toledo B.V., NL-4000 HA Tiel
Tel. +31-3-4463 8363, Fax +31-3-4463 8390
PL Mettler-Toledo, Sp. z o.o., PL-02-929 Warszawa
Tel. +48-22-651 92 32, Fax +48-22-651 71 72
RU Mettler-Toledo C.I.S. AG, 10 1000 Moscow
Tel. +7-095-921 92 11, Fax +7-095-921 63 53
SE Mettler-Toledo AB, S-12008 Stockholm
Tel. +46-8-702 50 00, Fax +46-8-642 45 62
SG Mettler-Toledo (S) Pte. Ltd., Singapore 139944
Tel. +65-7786 779, Fax +65-7786 639
SK Mettler-Toledo, SK-82104 Bratislava
Tel. +421-7-4342 7496, Fax +421-7-4333 7190
SI Mettler-Toledo, d.o.o., SI-1236 Trzin
Tel. +386-61-162 18 01, Fax +386-61-162 17 89
TH Mettler-Toledo (Thailand) Ltd., Bangkok 10310
Tel. +66-2-719 64 80, Fax +66-2-719 64 79
TW Mettler-Toledo Pac Rim AG, Taipei
Tel. +886-2-2579 5955, Fax +886-2-2579 5977
UK Mettler-Toledo Ltd., Leicester, LE4 1AW
Tel. +44-116-235 70 70, Fax +44-116-236 63 99
US Mettler-Toledo, Inc., Columbus, OH 43240
Tel. +1-614-438 4511, Fax +1-614-438 4900

For all other countries: Subject to technical changes


Mettler-Toledo GmbH © 01/04 Mettler-Toledo GmbH, ME-xxxxxxxx
PO Box, VI-400, CH-8606 Greifensee, Schweiz Printed in Switzerland on 100% chlorine-free
Tel. (01) 944 22 11, Fax (01) 944 31 70 paper, for the sake of our environment.

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