28 ElectroplatingElectronics

METTLER TOLEDO Titrators
Electronics and
electroplating applications
Application brochure 28
Dear Reader
Information technology and electronics have become increasingly relevant in our society
deeply influencing every aspect of our life. In particular, the world of communication has
experienced the largest transformation: thanks to powerful computers, Internet and mobile
phones the way of communicating has become faster, and an exponentially increasing
amount of information has become available.
If software is the soul of electronics devices, hardware represents their body. They can
smoothly function if their components such as printed circuits meet the required quality
standards. The production quality can be monitored by a variety of analytical techniques.
Titration is one analytical method used in electroplating and electronics industry to mainly
control the metal ion content and the degree of acidity of electroplating baths.
42 different methods covering various determinations in the electroplating analysis

are presented in this brochure, a representative collection of widely used titrations in the
electroplating and electronics industry.
These applications are the result of the efforts of many people. First we would like to mention
our former Applications Chemist Kees Mooibroek. His work from the previous application
brochure 4 “electroplating” was included in the present brochure, and completed with the
applications on titration of gold and silver. From collaboration with customers and our selling
organizations we were able to get additional methods, and Applications chemists extensively
tested the applications in the Market Support Laboratory.
We are proud to present to you our brochure on applications in the electroplating and
th
electronics industry containing valuable information and practical hints. This is the 28
brochure of a long series of comprehensive applications, which continues the tradition started
since the early 1970’s to focus on analytical competence in Market Support Group.
We wish you a lot of success
Craig Gordon Cosimo A. De Caro

Manager Market Supporrt AnaChem Applications Chemist
Contents
M062 Electroless copper bath: Determination of copper ....................................................... 4
M063 Electroless copper bath: Determination of free complexing agents ............................. 6
M064 Electroless copper bath: Sodium hydroxide and formaldehyde ................................... 8
M065 Electroless nickel bath: Determination of sodium hypophosphite ............................. 12

M066 Electroless nickel bath: Determination of nickel ....................................................... 16
M067 Electroless nickel bath: Determination of sodium orthophosphite ............................ 18
M151 Determination of acetic, phosphoric and nitric acid in a mixture .............................. 20

M152 Nitric, acetic and phosphoric acid mixture: large excess of phosphoric acid ............ 22
M153 Nitric, acetic and phosphoric acid mixture: concentrations below 0.3% ................... 24
M154 Simultaneous titration of HCl, CH3COOH, and NH4Cl ............................................. 26
M155 Polishing bath: determination of sulfuric and phosphoric acid .................................. 28
M156 Determination of boric acid in acidic mixtures of HCl and HF ................................. 30
M157 Determination of hydrochloric and nitric acid ........................................................... 34
M158 Determination of ammonia and hydrogen peroxide ................................................... 36
M159 Determination of hydrochloric acid and hydrogen peroxide ..................................... 38
M181 Back-titration of aluminum in acidic bath.................................................................. 40

M182 Titration of sulphuric and aluminum in an electroplating bath .................................. 42
M183 Determination of nickel and cadmium by complexometry ........................................ 44

M184 Determination of cadmium in alkaline bath ............................................................... 46
M185 Iodometric titration of Cr(VI) in an electroplating bath ............................................. 48

M186 Determination of Cr(III) by back-titration in an electroplating bath ........................ 50
M187 Chromium and vanadium in a K2Cr2O7 / V2O5 mixture ............................................. 52
M188 Determination of Cr(VI) in an electroplating bath by Fe(II) titration ........................ 54
M189 Determination of free cyanide in a copper bath ......................................................... 56
Page 2/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications
M190 Determination of free cyanide in a cyanidic zinc bath ............................................... 58
M191 Back-titration of zinc in a cyanidic zinc bath ............................................................. 60
M175 Titration of gold -Au(III)- in a standard solution ....................................................... 62

M208 Determination of gold by precipitation reaction with hydroquinone ......................... 64
M209 Titer determination of cerium sulfate vs. hydroquinone ........................................... 66
M210 Standardization of hydroquinone with pure gold ....................................................... 68
M179 Determination of the gold content in alloy................................................................. 72
M180 Determination of the approximate gold content content in alloys ............................. 75
M192 Determination of lead(IV) in batteries ...................................................................... 76

M193 Complexometric titration of lead in alloy .................................................................. 78
M194 Determination of nickel in an electroplating bath ...................................................... 80
M195 Determination of silver in silver alloy........................................................................ 82

M196 Determination of free potassium cyanide in a silver bath .......................................... 84
M197 Titration of Tin(II) in acidic tin bath .......................................................................... 86
M198 Photometric titration of zinc in a spin bath ................................................................ 88

M199 Determination of sulphate in a spin bath by precipitation titration ............................ 90
M200 Titration of fluoride in soldering salts ........................................................................ 92

M201 Standardization of 1/2 Pb(NO3)2 ............................................................................... 94
Literature
Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 3/100
METTLER TOLEDO
M062 Electroless copper bath: Determination of copper
Sample: Electroless copper bath 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
3.534 g/L CuSO4
3.512 g/L CuSO4
3.504 g/L CuSO4
3.449 g/L CuSO4
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
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
Number samples . . . . . . . . . . 5
ide, formaldehyde, weakly complexed copper, free
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 . . . . . . . . . mL
Volume [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 thio-
Limit A [mV, pH,...] .
Limit B [mV, pH,...] .
.
.
.
.
.
.
.
.
800.0
0.0
cyanate (KSCN) are added.
Maximum volume [mL] . . . . . . . 20.0
Termination after n EQPs . . . . Yes 4) Cu(II) is reduced with excess iodide (I-) and sub-
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard sequently precipitated as CuI in the presence of
Calculation
Result name . . . . . . . . . . . . Copper (Cu) thiocyanate (SCN-). KSCN is added to avoid ad-
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R1=Q*C1/U
C1=63.546/z
sorption of I2 on the surface of CuI :
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 3 2 Cu2+ + 4 I - → 2 CuI + I2
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) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes 2 S2O32- + I2 → S4O62- + 2 I-
Rel. standard deviation srel . . . . Yes
Outlier test . . . . . . . . . . . . Yes • Stir moderately. Vigorous stirring causes loss of
Record
Output unit . . . . . . . . . . . . Printer I2
All results . . . . . . . . . . . . Yes
• Alternative: Photometric indication with DP550
Phototrode; indicator: starch
Literature • Titration time: approx. 4 minutes
1. B. Bressel, Ausserstromloser Kupferelekrolyt,
DGO Deutsche Gesellschaft für Galvano- und
Oberflächentechnik e.V., Horionplatz 6, Düssel-
dorf (Germany), 1988
2. Copper bath's manufacturer
Disposal
Copper solutions: special waste
Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators. Author: Kees Mooibroek
METTLER TOLEDO
M063 Electroless copper bath: Determination of free complexing agents

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
METTLER DL70 Titrator Mettler-Toledo AG

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

STATISTICS
Mean value x = 20.407 mmol/L Free Compl.
Standard deviation s = 0.0089 mmol/L Free Compl.
Outlier test : sample No. 1/3
Statistics without sample No. 1/3

Mean value x = 20.411 mmol/L Free Compl.
Standard deviation s = 0.0029 mmol/L Free Compl.
Method Remarks
Method 063 Free Complexing Agents
Version 23-Jul-1991 15:25 Bath composition
Title
Method ID . . . . . . . . . . . . . 063
• This bath is used for chemical copper deposition
Title . . . . . . . . .
Date/time . . . . . . . . .
. . . . Free Complexing Agents
. . . . 23-Jul-1991 15:25
on printed circuit boards. It consists of sodium hy-
Sample droxide, formaldehyde, weakly complexed copper,
Number samples . . . . . . . . . . 5
Titration stand . . . . . . . . . . Stand 1 free complexing agent(s), and additives.
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 [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 40
. . . . 10
• The free complexing agents influence the rate of
Titration copper deposition and the stability of the bath.
Titrant . . . . . . . . . . . . . . CuSO4-(2)
Sensor . . . . . . . . . . . . . . DP550
Unit of meas . . . . . . . . . . . . mV Sample preparation
Titration mode . . . . . . . . . . . EQP
Predispensing 1 . . . . .
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
mL
0.0
1) The copper bath is diluted and then titrated with
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] . . . . . . .
t(min) [s] . . . . . .
.
.
.
.
.
.
.
.
2.0
3.0 2) It is recommended to use a trituration 1:500 mu-
t(max) [s] . . . . . .
Threshold . . . . . . .
.
.
.
.
.
.
.
.
30.0
100.0
rexide: NaCl.
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 . . . . Yes
n = . . . . . . . . . . . . . 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-
E - V curve . . . . . . . .
. . . . Yes
. . . . Yes
tion in alkaline solution:
Statistics Cu 2+ + Agent → Cu-Agent 2+
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes At the equivalence point (simplified):
Outlier test . . . . . . . . . . . . Yes Cu 2+ + Murexide - → Cu-Murexid + (violet-yellow)
Record
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, Düssel- • A fixed predispensing shortens the titration time.
dorf (Germany), 1988. • Titration time: approx. 4 minutes.
E-V curve
Disposal
Other titrators
DL50 Graphix, DL53/55/58, DL77 titrators.
Author: Kees Mooibroek

METTLER TOLEDO
M064 Electroless copper bath: Sodium hydroxide and formaldehyde

Substance: Sodium hydroxide, formaldehyde
Method: 064
Preparation: Deionised water, 40 mL
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
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
14.55 g/L NaOH
14.62 g/L NaOH
14.51 g/L NaOH
14.52 g/L NaOH
0.09 g/L Correction
STATISTICS
Mean value x = 12.2 pH Dil. sample
STATISTICS
Mean value x = 14.56 g/L NaOH
Standard deviation s = 0.047 mmol/L
Outlier test : no outliers!
STATISTICS
Mean value x = 8.58 g/L Formaldehyde
Standard deviation s = 0.109 g/L Formaldehyde
Outlier test : no outliers!
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 . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R5=8.5-(Q[2]*C5/U)
C5=30.03/1
8
Sample
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
Titrant . . . . . . . . . . . . . . HCl
> . . . . . . . . . . . . .
> . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
too low
***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
Result name . . . . . . . . . . . . Correction
Output unit . . . . . . . .
All results . . . . . . . .
. . . . Printer
. . . . Yes
Formula . . . . . . . . . . . . . . R3=14-(Q1*C3)/U
Constant . . . . . . . . . . . . . . C3=40/1
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Record
Remarks
Result last sample . . . . . . . . . Yes • The electrode DG111-SC is calibrated in the
E - V curve . . . . . . . . . . . . Yes
4 Dispense range of pH 9 to 12 (see application M004).
Titrant . . . . . . . . . . . . . . Na2SO3 (pH 10.5)
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
Sensor . . . . . . . . . . . . . . DG111-SC-(2)
complicated blank evaluations are necessary.
Unit of meas . . . . . . . . . . . . As installed
Titration mode . . . . . . . . . . . EP
Predispensing . . . . . . . . . . mL
• Total analysis time: approx. 4 minutes.
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
Condition . . . . . . . . . . . . Yes
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 rea-
gent 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 concetra-
tion 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.
E-V curve: NaOH content E-V curve: Formaldehyde content
Literature
1. B. Bressel, Ausserstromloser Kupferelekrolyt, DGO Deutsche Gesellschaft für Galvano- und Ober-
flächentechnik e.V., Horionplatz 6, Düsseldorf (Germany), 1988
Disposal
Other titrators
DL77 titrator.

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

35.01 g/L NaH2PO2•H2O
1/2 Chem.Ni 13/45 3.0 mL 28.93 g/L NaH2PO2
1/3 Chem.Ni 13.50 3.0 mL 29.10 g/L NaH2PO2
STATISTICS
Mean value x = 29.07 g/L NaH2PO2
STATISTICS
Mean value x = 35.02 g/L NaH2PO2•H2O
Standard deviation s = 0.150 g/L NaH2PO2•H2O
Outlier test: no outliers!
STATISTICS
Mean value x = -9.02 g/L Correction
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
Sensor . . . . . . . . . . . . . . DM140-SC 1) 2 mL sample are diluted with 50 mL sulphuric
Unit of meas . . . . . . . . . . . . mV
Titration mode . . . . . . . . . . . EQP acid solution 20%.
Volume [mL] . . . . . . . . . 0.0
Titrant addition . . . . . . . . DYN 2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
∆E(set)[mV] . . . . . . . . . 8.0
Limits ∆V . . . . . . . . . . Relative dispensed with a burette ("Titrant 1") to the
∆V(min) [%dosVol] . . . . . 0.5
∆V(max) [%buVol]. . . . . . 2.5 acidified sample using the auxiliary function
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 1.0 "Dosing" of the titrator. After dispensing cover
∆t [s] . . . . . . . . . . . 3.0
t(min) [s] . . . . . . . . . . 3.0 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,...] .
.
.
.
.
.
.
.
.
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
Calculation
. . . . Standard
I2 + H2PO2- + H2O = 2I- + HPO32- +3H+
Result name . . . . . . . . . . . . NaH2PO2
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R1=(H3-Q1)*C1/U
C1=M/z
The reaction requires 60 minutes to com-
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
g/L
2
plete.
Calculation
Result name . . . . . . . . . . . . NaH2PO2•H2O 4) Oxidising agents stronger than iodine may
Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U
Constant . . . . . . . . . . . . . . C2=105.99/z cause side reactions with organic bath compo-
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 nents or decomposition products.
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
Correction
R3=26-((H3-Q1)*C3/U) 5) The amount of substance of the dispensed io-
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C3=105.99/1
g/L dine solution is determined with method 065b
Instruction
. . . . 2
(see next page).
Instruction . . . . . . . . . . . . Sodium hypophosphite
> . . . . . . . . . . . . . . . . . monohydrate content
> . . . . . . . . . . . . . . . . . too high.Pls.correct
Condition . . . . . . . . . . . . . Yes Content determination (Method 065a)
Condition . . . . . . . . . . . R2>29
Instruction
Instruction . . . . . . . .
> . . . . . . . . . . . . .
.
.
.
.
.
.
.
.
Sodium hypophosphite
monohydrate content
1) The content of sodium hypophosphite is deter-
> . . . . . . . . . . . . .
Condition . . . . . . . . .
.
.
.
.
.
.
.
.
too low.Pls.correct
Yes
mined by an iodometric backtitration. Excess
Record
Condition . . . . . . . . . . . R2<23 iodine is dispensed (sample preparation) in
Output unit . . . . . . . .
.
.
.
.
.
.
.
.
Printer
Yes
order to oxidise hypophosphite in the acidic
Table of measured values . .
E - V curve . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes
solution. The remaining excess iodine is ti-
Statistics
Ri (i=index) . . . . . . . . . . . . R1
trated with sodium thiosulphate:
Statistics
Ri (i=index) . . . . . . . . . . . . R2 I2 + 2 S2O32- → 2I- + S4O62-
Standard deviation s . . . . . . . . Yes
Outlier test . . . . . . . . . . . . Yes 2) Sodium thiosulphate is standardized with po-
Statistics
Ri (i=index) . . . . . . . . . . . . R4 tassium iodate (see application M009).
Rel. standard deviation srel
Outlier test . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes 3) The titrator displays warnings if upper or lower
Statistics
Ri (i=index) . . . . . . . . . . . . R3 result limits are exceeded.
Record
All results . . . . . . . . . . . . Yes
Results and table of measured values
065a Hypophosphite in Chem.Ni measured 18-Nov-1991 15:19

RESULTS

SAMPLE
No. 1/4
Titration stand Stand 1
Identification Chem.Ni 13.55
Volume U = 3.0 mL
Correction factor f = 1.0
MEASURED VALUES
Titrant Na2S2O3 0.1 mol/L t = 0.99896
Drive Drive 2 20 mL
Sensor DM140-SC
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
Method 065b / Iodine solution Remarks
Method 065b Aux. value for M065/M067
Title
Sample preparation Method 065b
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 . . . . . .
Entry type . . . . . . . . .
.
.
.
.
.
.
.
.
Stand 1
Fixed volume U
2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.0
********
dispensed automatically by the titrator using
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
0.0
1
the function "Dispense" in method 065b.
Stir
Speed [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . .
Dispense
. . . . 5
Titration
Titrant . . . . . . . . . . . . . . 1/2 I2
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 potas-
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
.
.
.
.
.
.
.
.
DM140-SC
mV
sium iodate (see application M009).
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
mL
15.0
3) The mean value of a series of three sample is
∆E(set)[mV] . . . . .
.
.
.
.
.
.
.
.
DYN
4.0
automatically stored as auxiliary value H3 and
Limits ∆V . . . . . .
∆V(min) [%dosVol] .
.
.
.
.
.
.
.
.
Relative
0.1
can therefore by applied by method 065a for
∆V(max) [%buVol]. .
Measure mode . . . . . .
.
.
.
.
.
.
.
.
1.5
EQU
the determination of nickel.
∆E [mV] . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . 3.0 4) The storage of the mean value only occurs if
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 it is comprised between the limits 1.5 and 2.5
Threshold . . . . . . . . . . . 150.0
EQP range . . . . . . . . . . . Yes mmol which assure an adequate cocnentra-
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . -1000.0 tion.
n = . . . . . . . . . . . . . 1 5) The shelf life of the iodine solution is limited.
Evaluation procedure . . . . . . Standard
Calculation We recommend to perfom method 065b before
Result name . . . . . . . . . . . . Consumption
Formula . . . . . . . . . . . . . . R1=Q1
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mmol
Decimal places . . . . . . . . . . . 4
Record
Results last sample . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Auxiliary value
ID text . . . . . . . . . . . . . . Aux.M065/M067
Formula . . . . . . . . . . . . . . H3=�[1]
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . 1.5<�<2.5
Record
All results . . . . . . . . . . . . Yes
Method 065b / Iodine concentration
Disposal
Nickel solutions: special waste
Other titrator
DL77 titrator.
METTLER TOLEDO
M066 Electroless nickel bath: Determination of nickel
Sample: Electroless nickel bath Instruments: METTLER TOLEDO DL70

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

STATISTICS
Mean value x = 5.74 g/L Ni Content
Standard deviation s = 0.012 g/L Ni Content
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 . . . . . . . . .
Title . . . . . . . . .
. . . . 066
. . . . 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 . . . . . .
.
.
.
.
.
.
.
.
6
Stand 1
range: 25-500 mg 1:500 murexide : NaCl trituration
Entry type . . . . . . . . .
Volume [mL] . . . . . . .
.
.
.
.
.
.
.
.
Fixed volume U
5.0
pe sample).
ID1 . . . . . . . . . . . . . . . . ********
Molar mass M . . . . . . . . . . . . 58.69 • The results are given in g/L using the molar mass
Stir M.
Speed [%] . . . . . . . . . . . . . 60
Time [s] . . . . . . . . . .
Titration
. . . . 10 M(Ni) = 58.69 g/mol
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.
Volume [mL] . . . . . . . . . 1.0 • Nickel ions forms a yellow complex with murexide
Titrant addition . . . . . . . . DYN
∆E(set)[mV] . . . . . . . . . 8.0 in alkaline solution:
Limits ∆V . . . . . . . . . . Absolute
∆V(min) . . . . . .
∆V(max) . . . . . .
.
.
.
.
.
.
.
.
0.05
0.2 Ni 2+ + Murexide - = Ni-Murexide+
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . .
∆t [s] . . . . . . .
.
.
.
.
.
.
.
.
2.0
2.0
By adding EDTA, Ni forms a more stable complex
t(min) [s] . . . . . . . . . . 2.0 with EDTA:
t(max) [s] . . . . . . . . . . 15.0
Threshold . . . . . . . . . . . 10.0
EQP range . . . . . . . . . . . Yes Ni-Murexide+ + EDTA 4- = Ni-EDTA2-+ Murexide-
Limit A [mV, pH,...] . . . . . 1000.0
.
.
.
.
.
.
.
.
0.0
20.0
At the equivalence point, all Ni ions have been
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 / %
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
Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77.
METTLER TOLEDO
M067 Electroless nickel bath: Determination of sodium orthophosphite
Sample: Electroless nickel bath Standard: For Na2S2O3 : Potassium iodate

0.5 mL
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
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
156.57 g/L NaH2PO3
123.47 g/L H3PO3
156.69 g/L NaH2PO3
123.57 g/L H3PO3
156.88 g/L NaH2PO3
123.71 g/L H3PO3
156.83 g/L NaH2PO3
123.67 g/L H3PO3
156.73 g/L NaH2PO3
123.60 g/L H3PO3
156.41 g/L NaH2PO3
123.35 g/L H3PO3
156.80 g/L NaH2PO3
123.65 g/L H3PO3
STATISTICS
Mean value x = 189.86 g/L Na2HPO3
Standard deviation s = 0.196 g/L Na2HPO3
STATISTICS
STATISTICS
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 . . . . . . . . .
Date/time . . . . . . . . .
. . . . Orthophosphite in Chem.Ni
. . . . 21-Nov-1991 12:44 The bath must be replaced as soon as a specific
Sample
Number samples . . . . . . . . . . 8
concentration is reached.
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.5
********
Sample preparation (Method 067)
Molar mass M . . . . . . . . . . . . 0.0
Dispense
. . . . 2
1) Add 20 mL 5% NaHCO3 to the sample.
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 [%] . . . . . . . . . . . . . 40
Time [s] . . . . . . . . . . . . . . 20 tor. Cover the beaker to prevent loss of iodine.
Titration
Titrant . . . . . . . . . .
.
.
.
.
.
.
.
.
Na2S2O3
0.1
3) This oxidation is carried out at room temperature
Sensor . . . . . . . . . . . . . . DM140-SC in the dark during 30 minutes :
Unit of meas . . . . . . . . . . . . mV
Predispensing 1 . . . . . . . . . mL I2 + HPO32- + 3 OH - = 2I- + PO43- + 2 H2O
Volume [mL] . . . . . . . . . 0.0
∆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 similar
Threshold . . . . . . . . . . . 150.0
EQP range . . . . . . . . . . . Yes method as 067. The result (mmol) is stored as aux-
Limit A [mV, pH,...] . . . . . 1000.0
Limit B [mV, pH,...] . . . . . -1000.0 iliary value H3 and used for the back-titration.
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
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C1=125.9589/z
g/L
067.
Decimal places . . . . . . . . . . . 2
Calculation • If the orthophosphite concentration exceeds the
Result name . . . . . . . . . . . . NaH2PO3
Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U limit of 200 g/L an instruction is displayed.
Constant . . . . . . . . . . . . . . C2=103.9768/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Calculation
Result name . . . . . . . . . . . . H3PO3 Nickel content of different baths
Formula . . . . . . . . . . . . . . R3=(H3-Q1)*C3/U
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C3=81.9947/z
g/L
Bath n Content/ g/L srel/%
Decimal places . . . . . . . . . . . 2
Instruction 28/10 A 3 189.00 0.158
Instruction . . . . . . . . . . . . CHECK CONCENTRATION
> . . . . . . . . . . . . . . . . . OF PHOSPHITE 28/10 B 8 189.66 0.103
> . . . . . . . . . . . . . . . . .
Disposal
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . R2>200
Record
Output unit . . . . . . . . . . . . Printer Nickel solutions: special waste
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
E-V curve
Outlier test . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Record
All results . . . . . . . . . . . . Yes
Other titrators
DL53/DL55 (without Function "Instruction"),
DL58, DL77. Author: Kees Mooibroek
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
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
3 Mix. Acid 1.0 mL
STATISTICS
Mean value x = 0.9598 mol/L HAc content
Standard deviation s = 0.00824 mol/L HAc content
STATISTICS
Mean value x = 0.9862 mol/L H3PO4 content
Standard deviation s = 0.00300 mol/L H3PO4 content
STATISTICS
Mean value x = 0.4429 mol/L HNO3 content
Standard deviation s = 0.00384 mol/L HNO3 content
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 . . . . . . . . . . . . . Mix
Title . . . . . . . . . . . . . HAc+HNO3+H3PO4 2. H3PO4 = H+ + H2PO4-
Date/time . . . . . . . . . . . . . 21-Nov-1991 12:44
Sample 3. HAc = H+ + Ac-
Sample ID . . . . . . . . . . . . . Mix. Acid
Entry type . . . . . . . . . . . . . Fixed volume 4. H2PO4 = -
H + HPO42-
+
Volume [mL] . . . . . . . . . . . 1.0
Molar mass M . . . . . . . . . . . . 100
Titration stand . . . . . . . . . . ST20A Due to the little difference between the pKa-
Pump . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H 2O 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
Pump . . . . . . . . . . . . . . No
Rinse . . . . . . . . . . . . . . Yes distinguished. Therefore only three potential
Solvent . . . . . . . . . . . H 2O
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 method
Time [s] . . . . . . . . . . . . . . 10
EQP titration for a fully automatic procedure. The method
Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH can be easily modified for manual operation:
Concentration [mol/L] . . . . . . 0.1
Sensor . . . . . . . . . . . . . DG111 enter "Stand 1" as titration stand in the function
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . to volume 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] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
1.0
1.0
Neutralization with hydrochloric acid.
t(min) [s] . . . . . . . . . . . 2.0
t(max) [s] . . . . . . . . . . . 10.0
Recognition
Threshold . . . . . . . . . . . . 17.0 Other titrators
Steepest jump only . . . . . . . No
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
None
DL50 Graphix, DL53/DL55, DL70ES, DL77.
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
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
Preparation: 50 mL deion. water Peristaltic pump ME-65241
(dispensed by pump)
Indication: DG111-SC
Titrant: Sodium hydroxide, NaOH
c(NaOH) = 1 mol/L

Results: Method
Measured
2.2 EQP Titration
07/17/2000 14:48
07/17/2000 13:59
User YY
ALL RESULTS
1 0.5102 g
R1 = 3.0723 % HNO3 content
R2 = 12.2359 % HAc content
R3 = 70.9786 % H3PO4 content
2 0.5199 g
R3 = 70.8494 % H3PO4 content
3 0.518 g
R3 = 70.9050 % H3PO4 content
4 0.5373 g
R3 = 70.7380 % H3PO4 content
5 0.5176 g
R3 = 70.7452 % H3PO4 content
6 0.5078 g
R3 = 70.6551 % H3PO4 content
STATISTICS
Mean value x = 3.0574 % HNO3 content
Standard deviation s = 0.05917 % HNO3 content
STATISTICS
Mean value x = 11.9131 % HAc content
Standard deviation s = 0.23308 % HAc content
STATISTICS
Mean value x = 70.8119 % H3PO4 content
Standard deviation s = 0.12031 % H3PO4 content
Method Remarks
Method 2.2 EQP Titration
Title
Version 07/17/2000 13:59
• This titration procedure includes four steps:
Method ID . . . . . . . . . . . . . 2.2
Title . . . . . . . . . . . . . EQP Titration 1. HNO3 = H+ + NO3-
Date/time . . . . . . . . . . . . . 07/17/2000 13:59
Sample 2. H3PO4 = H+ + H2PO4-
Sample ID . . . . . . . . . . . . .
Entry type . . . . . . . . . . . . . Weight 3. HAc = H+ + Ac-
Lower limit [g] . . . . . . . . . 0.4
Upper limit [g] . . . . . .
Molar mass M . . . . . . . . .
.
.
.
.
.
.
0.6
98
4. H2PO4- = H+ + HPO42-
Titration stand . . . . . . . . . . ST20A
Pump . . . . . . . . . . . . . . Yes Due to the little difference between the pKa-value
Solvent . . . . . . . . . . . H 2O
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 . . . . . . . . . . . H 2O 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 . . . . . . . . .
Temperature sensor . . . . . .
.
.
.
.
.
.
No
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.
Sensor . . . . . . . . . .
.
.
.
.
.
.
1.0
DG111
The values are then used for sample analysis.
Unit of meas. . . . . . . .
Predispensing . . . . . . . .
.
.
.
.
.
.
pH
to volume
Note that these values depend on the concentration
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
∆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
Other titrators
Termination
at potential . . . . . . . . . . Yes
Potential [mV, pH,..] . . . . 10.5
at slope . . . . . . . . . . . . No DL50 Graphix, DL53/DL55, DL70ES, DL77.
after number EQPs . . . . . . . . Yes
n = . . . . . . . . . . . . . 1
comb. termination criteria
Evaluation
. . . Yes E-V curve
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)
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

c(NaOH) = 0.1 mol/L

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
STATISTICS
Mean value x = 0.0940 % Nitric Acid
Standard deviation s = 0.001711 % Nitric Acid
STATISTICS
Mean value x = 0.1168 % Acetic Acid
Standard deviation s = 0.001026 % Acetic Acid
STATISTICS
Mean value x = 0.2509 % Phosphoric
Standard deviation s = 0.000804 % Phosphoric
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-
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
10.0
Due to the little difference between the pKa-value
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
98
1
of HNO3 and H3PO4 , the first two steps can not be
Temperature sensor . . . . . . . . . Manual distinguished. Therefore only three potential jumps
Stir
Speed [%] . . . . . . . . . . . . . 50 can be seen on the titration curve.
Time [s] . . . . . . . . . . . . . . 10
Titration
Titrant . . . . . . . . . .
.
.
.
.
.
.
.
.
NaOH
0.1 • The potential jumps are evaluated by means of
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DG111-SC
mV control ranges. To set the optimum values for the
.
.
.
.
.
.
.
.
EQP
mL
control ranges, a trial titration must be first per-
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
0
DYN
formed. From the table of measured values the ap-
∆E(set) [mV] . . . . . . . . . 8.0 propriate control ranges can be selected and stored
∆V(min) [mL] . . . . . . . 0.05 in the method.
∆V(min) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU Note that these values depends on the concentration
∆E [mV] . . . . . . .
∆t [s] . . . . . . .
.
.
.
.
.
.
.
.
0.2
1.0 of the sample and on sample preparation. Thus, it
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
3.0
30.0
is necessary to first determine these values for any
Threshold . . . . . . . .
.
.
.
.
.
.
.
.
40.0
10.0
other acid mixture.
n = . . . . . . . . . . . . . 4
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 . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R2=Q(100>EPOT>-80)*C2
C=60/(U*10*z) E-V curve
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 4
Calculation
Result name . . . . . . . . . . . . Phosphoric
Formula . . . . . . . . . . . . . . R3=Q(EPOT<-100)*C3/U
Constant . . . . . . . . . . . . . . C=M*3/(10*3)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 4
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Record
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)
METTLER TOLEDO
M154 Simultaneous titration of HCl, CH3COOH, and NH4Cl
Sample: 3 mL acid mixture Standard: Potassium hydrogen phtalate

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

Peristaltic pump ME-65241
c(NaOH) = 0.1 mol/L Indication: DG111-SC
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%
Method Remarks
Method WS2 HCl/HOAc/NH4Cl
Version Sep/10/1999 9:49 am
Title • A mixture of three different acids (hydrochloric

Method ID . . . . . . . . .
Title . . . . . . . . . . .
. . . . WS2
. . . . HCl/HOAc/NH4Cl acid, acetic acid and ammonium chloride) with
Date/time . . . . . . . . .
Sample
. . . . Sep/10/1999 9:49 am
clear different acid dissociation constant (pKa
Number samples . . . . . . .
.
.
.
.
.
.
.
.
6
ST20 1 = -10, 4.75, and 9.25, respectively) is titrated
Entry type . . . . . . . . .
Lower limit [mL] . . . .
.
.
.
.
.
.
.
.
Volume U
0.5 with 0.1 M NaOH.
Upper limit [mL] . . . . . . . . 2.5
ID1 . . . . . . . . . . . . . . . . Serie2
Molar mass M . . . . . . . . . . . . 36.46
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
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DG111-SC deionized water before titration.
Unit of meas. . . . . . . . . . . . As installed
dE(set) [mV] . . . . . . . . . 8.0
Limits dV . . . . . .
dV(min) [mL] . . .
.
.
.
.
.
.
.
.
Absolute
0.03 • Reactions:
dV(max) [mL] . . .
.
.
.
.
.
.
.
.
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 . . . . . . . .
.
.
.
.
.
.
.
.
2.2
4.0 Dominating reaction in the pH-range 5.0-9.0:
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
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C1=M/(10*z)
mg/L 9.0-11.5:
Calculation
. . . . 3
NH4Cl + NaOH = Na+ + Cl- + NH3 + H2O
Result name . . . . . . . . . . . . HOAc
Formula . . . . . . . . . . . . . . R2=Q2*C2/U
Constant . . . . . . . . . . . . . . C2=60.0/(10*z)
Result unit . . . . . . . . . . . . mg/L
Decimal places . . . . . . . . . . . 3
Calculation
Result name . . . . . . . . . . . . NH4Cl
Formula . . . . . . . . . . . . . . R3=Q3*C3/U
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C3=53.49/(10*z)
mg/L Disposal:
Decimal places . . . . . . . . . . . 3
Record
---
E - V curve . . . . . . . . . . . . Yes
dE/dV - V curve . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 20.0
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Statistics
Ri (i=index) . . . . . . . . . . . . R2
Statistics
Ri (i=index) . . . . . . . . . . . . R3
Record
All results . . . . . . . . . . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL70ES. Authors: H.-J. Muhr, E. Renaud Gueletti, J.Zarske
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

c(NaOH) = 0.5 mol/L
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
1/1 0.1781 g Weight m

R2 = 29.04 % Sulfuric
1/2 0.1781 g Weight m
1/3 0.1781 g Weight m
STATISTICS
Mean value x = 48.99 % Phosphoric
Standard deviation s = 0.088515 % Phosphoric
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 added
Method ID . . . . . . . . . . . . . WS2
Title . . . . . . . . . . . . . . . H2SO4+H3PO4 in Polstar into the titration beaker together with 50 mL deion-
Date/time . . . . . . . . .
Sample
. . . . 21-02-1994 10:15
ized water.
Number samples . . . . . . . . . . . 3
Titration stand . . . . . . . . . . ST20 1
Entry type . . . . . . . . .
Lower limit [g] . . . . .
.
.
.
.
.
.
.
.
Weight m
0.0
• Sulfuric and phosphoric acid can dissociate two
Upper limit [mL] . . . . . . . . 2.0 protons H+ (sulfuric acid, H2SO4) and three protons
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 98 H+ (phosphoric acid, H3PO4), respectively.
Temperature sensor . . . . . . . . . Manual The dissociation constants pKa of H2SO4 are:
Stir
Speed [%] . . . . . . . . . . . . . 50 pKa1 = approx. -3,
Time [s] . . . . . . . . . . . . . . 10
Titration pKa2 = 1.92.
Titrant . . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . . 0.5 Sulfuric acid is a strong acid that dissociates com-
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DG111-SC
mV
pletely in water.
Predispensing 1 . . . .
.
.
.
.
.
.
.
.
EQP
mL
The dissociation constants pKa of H3PO4 are:
Volumen [mL] . . . .
.
.
.
.
.
.
.
.
0.1
DYN
pKa1 = 2.12
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
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 . . . . . . . .
.
.
.
.
.
.
.
.
%
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+ + SO42- + H2O
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
%
2
H3PO4 + NaOH = H2PO4- + Na+ + H2O
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Standard deviation s . . . . . . . . Yes 2nd EQP:
Record
H2PO4- + NaOH = HPO42- + Na+ + H2O
E - V curve . . . . . . . . . . . . Yes
Rinse
Auxiliary reagent . . . . . . . . . H2O
Volume [mL] . . . . . . . . . . . . 20.0
Disposal
E-V curve
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Authors: Application Laboratory MT-Germany
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

c(NaOH) = 0.1 mol/L
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
Method Remarks
Method A001 Borsäure • Sample preparation:
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
.
.
.
.
.
.
.
.
1
Stand 1
titration, mannitol is added to the sample. Mannitol
Entry type . . . . . . . . .
Lower limit [mL] . . . .
.
.
.
.
.
.
.
.
Weight m
0.05
forms a complex with boric acid giving in a medium
Upper limit [mL] . . . . . . . . 0.15 strong acidic compounds.
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 61.83
Stir • A sample changer ST20A can be used in this method
Speed [%] . . . . . . . . .
Time [s] . . . . . . . . . .
. . . . 50
. . . . 10
for a fully automatic procedure. The method can
Titration
Titrant . . . . . . . . . . . . . . NaOH
be easily modified for automatic operation: enter
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DG115-SC
"ST20 1" as titration stand in the function SAM-
Unit of meas. . . . . . . . . . . . mV PLE.
Predispensing . . . . . . . . . mL
Volume [mL] . . . . . . . . . 1.0
Titrant addition . . . . . . . . Dynamic • CAUTION: Hydrofluoric acid is poisonous! Work
∆E(set) [mV] . . . . . . . . . 8.0
∆V(min) [mL] . . . . . . . . . 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 . . . . . .
Potential [mV,pH,...].
.
.
.
.
.
.
.
.
EPA
0.0
Calculation
Result name . . . . . . . . . . . . mL HCl/HF E-V curve:
Formula . . . . . . . . . . . . . . R=VEQ[1]
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mL
Decimal places . . . . . . . . . . . 3 Titration of HCl/HF
Record
All results . . . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Dispense
Titrant . . . . . . . . . . . . . . Mannitol
Volume [mL] . . . . . . . . . . . . 20.0
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60
Titration
Titrant . . . . . . . . . . . . . . NaOH
Sensor . . . . . . . . . . . . . . . DG115-SC
Unit of meas. . . . . . . . . . . . mV
Volumen [mL] . . . . . . . . 1.0
∆E(set) [mV] . . . . . . . . . 8.0
∆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
Calculation
Result name . . . . . . . . . . . . mL Brsaeure
Formula . . . . . . . . . . . . . . R2=VEQ[2]
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . mL
Decimal places . . . . . . . . . . . 3
Record
All results . . . . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Author: Dieter Rehwald
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: 1 titration function:
st Printer EPSON FX850
1.1 Weigh 0.5 g of acid sample. with serial interface
1.2 Take 10 mL potassium fluo-
ride solution (KF, e.g. 10%) Method: HF1
and dilute it to 50 mL with (This method consists of two
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
determines the HF-content.
• Total acid strength:

Steel mainly contains iron, chromium and nickel and other metal ions. These metal ions can affect
the analysis, e.g. they can form hydroxide complexes due to the titrant addition of KOH.
Therefore, an excess of potassium fluoride solution is added to avoid interference. In fact, fluoride
ions form complexes with metal ions (e.g. Al), and thus, it can mask them.
• HNO3-content:
Hydrofluoric acid (HF) and nitric acid (HNO3) are both strong acids in aqueous solution (dissociation
constant pKa(HNO3) = -1.32 at 12.5°C; and pKa(HF) = 3.45), they dissociate completely. Since the
pKa values are close to each other, the two potential jumps can not be distinguished during titration
with a strong base in an aqueous solution: there is only one potential jump in the titration curve.
To discriminate the two potential jumps, the solvent is replaced by acetone, where the difference in
pKa values of the two acids is large enough to separate them. The first EQP of the second titration
function corresponds to nitric acid. Further addition of sodium sulphate, a well-known drying agent
due to its hygroscopic property, allows the achievement of a complete anhydrous environment.
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
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
Result last sample . . . . . . . . . Yes
E - V curve . . . . . . . . . . . . Yes
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Remarks
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
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 60 etches glass. Wear gloves and safety goggles.
Disposal

Other titrators
Author: Craig Gordon
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 con-
Preparation: method jud3: tent.
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
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
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
1 HCl/HNO3 1.011 g
R1 = 29.291 % HCl content
R2 = 2.676 % HNO3
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 . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . 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
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 Sec-
titrated with method amm1 ond burette DV1010
pH Option
Titrant 1: Sodium hydroxide, NaOH Titration beakers ME-101974
c(NaOH) = 1 mol/L
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
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
1 NH3/H2O2 0.662 g
R1 = 0.936 % H2O2 content
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 determina-
tion
3. Method hydr1: determination of HCl by redox Other titrators
titration with 1/5 KMnO4. DL50 Graphix, DL53/DL55, DL70ES, DL77.
Please note that both methods can be resumed in a Author: Judy Maag
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 Sec-
titrated with method hcl1 ond burette DV1010
pH Option
Titrant 1: Sodium hydroxide, NaOH Titration beakers ME-101974
c(NaOH) = 1 mol/L
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
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
1 HCl/H2O2 0.777 g
R1 = 2.075 % H2O2 content
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
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
Formula . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . . . . . Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No Statistics . . . . . . . . . . . . . No
Formula . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . .
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 determina-
tion Other titrators
3. Method hydr1: determination of H2O2 by redox DL50 Graphix, DL53/DL55, DL70ES, DL77.
titration with 1/5 KMnO4. Author: Judy Maag
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
Sample Al content Comments

Results:
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
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 . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
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.
Stir
Speed [%] . . . . . . . . . . . . . 50 Sample preparation
Time [s] . . . . . . . . . . . . . . 10
EQP titration 1) Add 20 mL deionized water to the sample.
Titrant/Sensor
Titrant . . . . . . . . . .
.
.
.
.
.
.
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] . . . . . . . .
Titrant addition . . . . . . .
.
.
.
.
.
.
5.0
INC
3) 20 mL 0.1 mol/L EDTA are dispensed using the
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.3
Equilibrium controlled
auxiliary function "Dosing" of the titrator.
∆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
Range . . . . . . . . . . . . . . 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
n = . . . . . . . . . .
.
.
.
.
.
.
1
No
Procedure
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 . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R=(H1-Q)*C/m
C=M/z
result (mmol) is stored as auxiliary value H1 and
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 . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
• Buffer solution pH 4: Dissolve 120 mL glacial
Statistics . . . . . . . . . .
Calculation
. . . No acetic acid (i.e. 100%) and 54 g sodium acetate
Formula . . . . . . . . . . . . . . trihydrate in a 1 L flask. Add 10 mL 0.05 mol/L
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 0 HgEDTA, 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 is
Raw results . . . . . . . . .
Table of measured values . . .
.
.
.
.
.
.
No
Yes
dissolved into the buffer solution instead of adding
Sample data . . . . . . . . .
E - V curve . . . . . . . . .
.
.
.
.
.
.
No
Yes three drops for each sample.
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . .
log ∆E/∆V - V curve . . . . .
.
.
.
.
.
.
No
No
Amalgamation of DM141 electrode (Hg-DM141)
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
.
.
.
.
No
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
excess mercury is wiped off. Several titrations can
Disposal be indicated before re-amalgamation.
The sample to be classified as special waste (Hg).
• Note: the Hg-DM141 is inactivated by hydrogen
peroxide, H2O2, and by S2-, CN- , .... .
Other titrators
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)
Preparation: 50 mL deionized water
Titrant: Sodium hydroxide, NaOH:
c(NaOH) = 1 mol/L

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
Method
Method 25002 Free acid + Al
Remarks
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 . . . . . . . .
Volume [mL] . . . . . .
.
.
.
.
.
.
.
.
.
.
Fixed volume
2.0
• The determination of free acid and aluminum in an
Molar mass M . . . . . . .
Equivalent number z . . .
.
.
.
.
.
.
.
.
.
.
26.98
3
acidic aluminun bath is determined with a single
Titration stand . . . . .
Temperature sensor . . . .
.
.
.
.
.
.
.
.
.
.
Stand 1
Manual
titration using sodium hydroxide.
Stir • The titration curve gives three equivalence
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 points:
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . NaOH
Concentration [mol/L] . . . . . . 1.0 1st EQP: Neutralization of free acid
Sensor . . . . . . . . . . . . . DG111
Unit of meas. . . . . . . . . . . As installed H2SO4 + 2 NaOH = Na2SO4 + 2 H2O
Predispensing . . . . . . . . . . . No
∆E(set) [mV] . . . . .
∆V(min) [mL] . . . . .
.
.
.
.
.
.
.
.
.
.
4.0
0.02 2nd EQP: Precipitation of aluminum hydroxide
∆V(min) . . . . . . . .
Measure mode . . . . . . .
.
.
.
.
.
.
.
.
.
.
0.2
Equilibrium controlled Al2(SO4)3 + 6 NaOH = 2 Al(OH)3 + 3 Na2SO4
∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . .
t(max) [s] . . . . . .
.
.
.
.
.
.
.
.
.
.
3.0
30.0
3rd EQP: Dissolution of Al(OH)3
Recognition
Threshold . . . . . . . . . . . . 4
Al(OH)3 + NaOH = Al(OH)4- + Na+
Range . . . . . . . . . . . . . . No
Tendency . . . . . . .
Termination
. . . . . Positive
Literature
at potential . . . . . . . . . . No • Application no. M531, in Application brochure 18,
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . No
Evaluation
Titration curves: standard solution

Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
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
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
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
Method Remarks
Method 40002 Ni + Cd
Version 12/01/2001 15:50 • The method was developed on the DL40 titrator (see
Title DL40 applications No. 317) and has been adapted
Method ID . . . . . . . . . . . . . 40002
Title . . . . . . . . . . . . . Ni + Cd 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:
Titration stand . . . . . . .
.
.
.
.
.
.
Stand 1
Manual
1) Add 10 mL buffer solution pH 10.
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.
Sensor . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
HgDM141
mV
4) Add 3 drops 0.05 mol/L HgEDTA.
Predispensing . . . . . . . . . . . Yes
Volume [mL] . . . . . . . . . . . 1.0 B) Ni determination:
Titrant addition . . . . . . . . . . INC
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.1
1) Add 10 mL buffer solution pH 10.
∆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
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Negative Procedure
Termination
at maximum volume [mL] . .
at potential . . . . . . .
.
.
.
.
.
.
20.0
No • Cd content:
at slope . . . . . . . . .
.
.
.
.
.
.
No
Yes 1) Ni is masked with dimethylglyoxime diso-
n = . . . . . . . . . .
.
.
.
.
.
.
1
No
dium salt. The sample is titrated with method
Evaluation
40002.
Potential 1 . . . . . . . .
Potential 2 . . . . . . . .
.
.
.
.
.
.
No
No
2) The Cd content is stored as auxil. value H6.
Condition . . . . . . . . . . neq=0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
• Ni content:
Constant . . . . . . . . . . .
Decimal places . . . . . . . .
.
.
.
.
.
.
C=M/z
3
1) EDTA forms complexes with both Ni and Cd.
Result unit . . . . . . . . . . . . g/L 2) To distinguish both metal ions, the Cd content is
Result name . . . . . . . . . . . . Cd Content
Statistics . . . . . . . . . . . . . Yes accounted for as a blank value in the calculation:
Calculation
Formula . . . . . . . . . . . . . . R2=Q R = (Q - H6)*C/m .
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3 3) Since nickel is determined, C = M(Ni)/z, and
Result unit . . . . . . . . . . . . mmol
Result name . . . . . . . . . . . . Cd Content therefore M = 58.59 .
Statistics . . . . . . . . . . . . . Yes
Auxiliary value
ID . . . . . . . . . . . . . . . . . mmol Cd
Constant . . . . . . . . . . . . . . H6=R2 Chemicals
Report
Output . . . . . . . . . . . .
Results . . . . . . . . . . .
.
.
.
.
.
.
Printer
No • Buffer solution pH 10: 70 mL of concentrated am-
All results . . . . . . . . .
Raw results . . . . . . . . .
.
.
.
.
.
.
Yes
No
monia solution (d=0.9 g/mL) and 70 g ammonium
Sample data . . . . . . . . .
.
.
.
.
.
.
Yes
No
chloride (or 110 g NH4NO3) are dissolved in a 1 L
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
.
.
.
.
.
.
Yes
Yes
flask with deionized water.
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No • 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No and 0.05 mol/L Hg-acetate are mixed together.
∆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- , .... .
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

R1 = 24.06 g/L Cadmium
STATISTICS
Mean value x = 23.73 g/L Cadmium
Standard deviation s = 0.560119 g/L Cadmium
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
Date/time . . . . . . . . .
Elektrolyt
. . . . 21-02-1994 9:48
M EDTA. No pH buffer is added, the bath is alka-
Sample line.
Number samples . . . . . . . . . . . 3
Entry type . . . . . . . . . . . . . Fixed volume U 2) Use a trituration 1:500 murexide: NaCl.
Volume [mL] . . . . . . . . . . . 1.0
ID1 . . . . . . . . . . . .
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
. 112.40
3) Add the indicator before starting analysis. Keep
Equivalent number z . . . . . . . . 1 sample free of air bubbles during titration. Air
Stir bubbles and undissolved impurities affect with the
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 photometric indication.
Titration
Titrant . . . . . . . . . . . . . . EDTA 4) Adjust the DP660 at 1000 mV in deionised water
Sensor . . . . . . . . . . . . . . . DP660 before starting titration (100% transmission).
Unit of meas. . . . . . . . . . . . mV
Predispensing 1 . . . . . . . . mL
Volume [mL] . . . . . . . . 0.5
dE(set) [mV] . . . . .
Limits dV . . . . . .
.
.
.
.
.
.
.
.
8.0
Absolute
Titration
dV(min) [mL] . . . . . . . 0.05
dV(max) [mL] . . . . . . . 0.2 • Cd(II) ions forms complexes with the indicator
Measure mode . . . . . . . . . . EQU
dE [mV] . . . . . . . . . . . 0.5 murexide in alkaline:
dt [s] . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . .
Threshold . . . . . . . .
.
.
.
.
.
.
.
.
30.0
50.0 Cd 2+ + Murexide - = Cu-Murexid +
n = . . . . . . . . .
.
.
.
.
.
.
.
.
1
Asymmetric
• By titration with EDTA, Murexide is diplaced
Rinse by EDTA and forms a complex with Cd ions in
Auxiliary reagent . . . . . . . . . H 2O
Volume [mL] . . . . . . . . . . . . 10.0 an alkaline, neutral or weakly acid medium:
Calculation
Result name . . . . . . . . . . . . Cadmium
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=Q*C/m
C1=M/z Cd 2+ + H2-EDTA2- = Cd-EDTA2- + 2 H+
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Statistics
Ri (i=index) . . . . . . . . . . . . R1
Record
Output unit . . . . . . . . . . . . Printer Disposal
All results . . . . . . . . . . . . Yes
Classify as special waste (heavy metals)
Application note:
Determination of Cd in a Cd-Ag alloy
Sample: 1.5 g Cd-Ag Alloy
Preparation: Add 20 mL HNO3 , boil to dissolve , cool E-V curve
to room temperature, fill up to 100 mL with deionized
water. To aliquots of 5 mL add 10 mL buffer ph 4.5
solution and 5 drops HgEDTA
Indication: HgDM141, HgEDTA
Titrant: EDTA, c(EDTA)=0.1 mol/L
Titration parameter: INC (0.1 mL), EQU (0.5 mV/2 s)
Calculation: Q*C/m; C = M/(10*z), M = 112.40
Lit.: DL40 appl. note 1986, Appl. Database 40.8603
Other titrators
DL50 Graphix, DL53/DL55, DL70ES, DL77. Authors: Application Laboratory MT-Germany
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
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
Mean value x = 150.24 g/L CrO3
Standard deviation s = 0.565 g/L CrO3
Method Remarks
Method vd03 Chromium (VI) in Cr-bath Sample preparation
1) 1 mL chromium bath is diluted with deionized wa-
Title ter to 10 mL. 1 mL aliquot corresponds to 0.1 mL
Method ID . . . . . . . . . . . . . vd03
Title . . . . . . . . . . . . . . . Chromium (VI) in Cr-bath original sample.
Date/time . . . . . . . . . . . . . 23-Nov-1989 12:04
Sample 2) 1 mL aliquot is diluted with 20 mL deion. water.
Number samples . . . . . . . . . . . 8
Entry type . . . . . . . . .
.
.
.
.
.
.
.
.
ST20
Fixed volume U
3) 10 mL sulfuric acid 1:1 are added.
Volume [mL] . . . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
4) Add 1.5 g potassium iodide (KI) and cover the bea-
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
99.99
3
kers to avoid loss of iodine.
Stir
Speed [%] . . . . . . . . . . . . . 60 5) The sample solution is kept in the dark during 5-10
Time [s] . . . . . . . . . . . . . . 10
Titration minutes.
Titrant . . . . . . . . . . . . . . Na2S2O3
Concentration [mol/L] . . . . . . . 0.1 6) During this time, Cr(VI) is reduced by excess io-
Sensor . . . . . . . . . . . . . . . DM140-SC
Unit of meas. . . . . . . . . . . . mV dide (I-) to Cr(III):
Predispensing . . . . . . . . . mL 2 Cr6+ + 6 I - → 2 Cr3+ + 3 I2 (z = 3)
Volume [mL] . . . . . . . . . 2.0
∆E(set) [mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0
The amount of iodine I2 formed is proportional to
Limits ∆V [mL] . . . . . . . . Absolute the Cr(VI) content.
∆V(min) [mL] . . . . . . . 0.02
∆V(max) [mL] . . .
.
.
.
.
.
.
.
.
0.2
EQU
Titration of iodine
∆E [mV] . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . 1.0 The formed I2 is then titrated with Na2S2O3:
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . .
.
.
.
.
.
.
.
.
300.0
20.0
2 S2O32- + I2 → S4O62- + 2 I-
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard • Stir moderately to avoid loss of I2
Calculation
Result name . . . . . . . . . . . . CrO3
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R=Q*C/U
C=M/z
Table of measured values:
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2
Rinse
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
2.200 0.200 293.3 -0.8 -4.2 0:23
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
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
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
4.535
0.020
0.021
168.6
160.8
-22.2
-7.8
-1108.1
-371.3
1:53
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
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 Printer EPSON LX400
M = 151.99 ; z = 3
Method: 40003
Preparation: - 10 mL nitric acid 1:1
- 50 mL 0.05 mol/L acid Accessories: Titration beakers ME-101446
cerium sulphate solution Peristaltic pump SP250
- 5 min. heating, 50°C 1 burette DV1020
Titrant: Sodium nitrite, NaNO2 Indication: DM140

c(1/2 NaNO2) = 0.2 mol/L
Standard: For cerium sulphate (see M543):

Di-sodium oxalate, C2Na2O4
For sodium nitrite (see M544):
Sulphanilic acid, C6H7NO3S
Results:
Sample Cr2O3 content Comments
Cr bath (g/L)
n = 2
x 4.2782 VEQ: 10.527 mL

srel -- DL40 Appl. no. 308
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 (see
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Cr(III) as Cr2O3
. . . 16/01/2001 10:10
DL40 applications No. 308) and has been adapted
Sample
Sample ID . . . . . . . . . . . . . Cr2O3
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 . . . . . . . . .
.
.
.
.
.
.
152
3
detemined by back titration after addition of excess
Titration stand . . . . . . . . . . ST20A cerium sulphate solution.
Pump . . . . . . . . . . . . . . No
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H 2O
Volume . . . . . . . .
Conditioning . . . . . . .
.
.
.
.
.
.
10.0
No
Sample preparation
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(Ce(SO4)2
Titrant . . . . . . . . . . . . . 1/2 NaNO2
Concentration [mol/L] . . . . . . 0.2 = 0.05 mol/L) are added by using the dispensing
Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . mV function of the titrator. This corresponds to 2.5
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.0 mmol/L equivalent Ce(IV)
Wait time [s] . . . . . . . . . . 0
∆V [mL] . . . . . . . . . .
.
.
.
.
.
.
Incremental
0.1 3) The sample solution is heated during 5 minutes at
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
0.5
50°C. During this time, Cr(III) is oxidized by ex-
∆t [s] . . . . . . . . . .
t(min) [s] . . . . . . . .
.
.
.
.
.
.
1.0
3.0
cess Ce (IV) to Cr(VI):
t(max) [s] . . . . . . . . . . . 30.0
Recognition 3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+ (z = 3)
Threshold . . . . . . . . . . . . 300
Range . . . . . . . . . . . . . . No whereas Ce(IV) is reduced to Ce(III):
Termination
at maximum volume [mL] . . . . . 20.0 Ce4+ → Ce3+ + e-
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No
n = . . . . . . . . . .
.
.
.
.
.
.
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
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
Constant . . . . . . . . . . . . . . C=M/(2*z)
Decimal places . . . . . . . . . . . 4 excess Ce(IV) using sodium nitrite as a titrant:
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Cr2O3
Statistics . . . . . . . . . . . . . Yes
Calculation 2Ce4+ + NO2- + Η2Ο → 2Ce3+ + NO3- + 2Η+
Formula . . . . . . . . . . . . . . R2=Q
Constant . . . . . . . . . . .
.
.
.
.
.
. 2
(z =2)
Result unit . . . . . . . . . . . . mmol
Result name . . . . . . . . . . . . Cr2O3
Statistics . . . . . . . . . .
Calculation
. . . Yes
Chemicals
Formula . . . . . . . . . . . . . . R3=VEQ
Constant . . . . . . . . . . .
.
.
.
.
.
. 3
• 0.05 mol/L acidic cerium sulphate solution: Either
Result unit . . . . . . . . . . . . mL 20.22 g Ce(SO4)2•4H2O or 31.63 g Ce(NH4)4(SO4)4•
Result name . . . . . . . . . . . . Titrant cons.
Statistics . . . . . . . . . . . . . Yes 2H2O are dissolved in 500 mL 1 mol/L sulphuric
Report
Output . . . . . . . . . . . . . . . Printer acid in a 1 L flask. Heat it p to 70°C in a water bath.
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes After cooling to room temperature, fill to the mark
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes with 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
brochure No. 18., "Standardization of Titrants",
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77. Author: P. Rast, MT Switzerland
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

Results:
K2Cr2O7 + V2O5 n srel K2Cr2O7 V 2O 5 n srel
Content (mmol) 0.86956 5 0.318 0.6195 0.25008 4 0.2079

aliquot
Total content (g) 0.3037 0.2274

(10 x aliquot)
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+ → 6 Fe3+ + 2 Cr3+ + 7 H2O
where
Cr2O72- + 14 H+ + 6 e- = 2 Cr3+ + 7 H2O
1.2 2 Fe2+ + V5+ = V4+ + Fe3+
2) V4+ to V5+:
5 V4+ + MnO4- + 8 Η+ = 5 V5+ + Mn2+ + 4 Η2O
3) 2nd FAS titration: see 1.2
Method
Method 25001 Cr/V
Remarks
Version 16/01/2001 15:30
Title
Method ID . . . . . . . . . . . . . 25001 (see DL25 appl. no. 21) and has been adapted for
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Cr/V
. . . 16/01/2001 15:30
the DL5x- and DL7x-titrators.
Sample
Sample ID . . . . . . . . . . . . . K2Cr2O7/V2O5 • The sample is dissolved in sulphuric acid. It is
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
25.0
oxidized with KMnO4 to ensure that chromium
Molar mass M . . . . . . . . .
.
.
.
.
.
.
294.26
6
and vanadium are present in their highest oxidation
.
.
.
.
.
.
Stand 1
Manual
state. The first titration with FAS gives the sum of
Stir
Speed [%] . . . . . . . . . . . . . 50
Cr and V in mmol. Iron (Fe(II)) reduces Cr(VI) to
Time [s] . . . . . . . . . . . . . . 10 Cr(III), while vanadium(V) is reduced to V(IV).
EQP titration
Titrant/Sensor In a second step , V(IV) is again oxidized by KMnO4
Titrant . . . . . . . . . . . . . FAS
Concentration [mol/L] . . . . . . 0.1 to V5+ and titrated with FAS. The difference between
Sensor . . . . . . . . . . . . . DM140
Unit of meas. . . . . . . . . . . mV the first and the second FAS titration accounts for
Predispensing . . . . . . . . . . . to volume
Volume [mL] . . . . . . . . . . . 2.0 the chromium content.
Wait time [s] . . . . . . . . . . 15
∆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% sulph-
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
0.5
1.0 uric acid until complete dissolution.
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
2) In a 250 mL flask dilute with deionized water.
Recognition
Threshold . . . . . . . . . . . . 200
3) Take 25 mL aliquots and add KMnO4 solution
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
dropwise (KMnO4: 5g/100mL).
Tendency . . . . . . . . .
Termination
. . . Negative 4) Add 5 mL conc. HCl to eliminate excess
at maximum volume [mL] . . . . . 20.0 KMnO4 present in the solution.
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No 5) Heat until violet permanganate colour disap-
n = . . . . . . . . . . . . . 1 pears, and cool to room temperature.
Evaluation 6) 1st titration with FAS (V2O5 + K2Cr2O7).
Potential 1 . . . . . . . . . . . No 7) Add again KMnO4 until violet is persistent.
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . 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.
Result unit . . . . . . . . .
.
.
.
.
.
.
5
mmol
10) 2nd titration with FAS (V2O5).
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
K2Cr2O7/V2O5
Yes
11) The difference between first and second result
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
gives the chromium content.
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 3
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Titrant cons. Chemicals
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . • 0.1 M Fe(NH4)2(SO4)2 • 6H2O (M=392.14):
Constant . . . . . . . . . . . . . .
Result unit . . . . . . . . .
.
.
.
.
. 0
.
Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
. No
mL flask with 10% sulphuric acid and fill to the
Report mark with deionized water.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . .
Raw results . . . . . . . . .
.
.
.
.
.
.
Yes
No
Literature
Sample data . . . . . . . . . . . . No • DL25 application no. 21, in DL25 Application
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . . . . . Yes Brochure "Chemicals", ME-51724629 (1994).
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No • Application no. M548 and M544, in Applica-
E - t curve . . . . . . . . . . . . No
V - t curve . . . . . . . . . . . . No tion brochure 18, "Standardization of Titrants",
∆V/∆t - t curve . . . . . . . . . . No
2000.
• "Metallurgische Analysen", József Mika, Buda-
pest
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
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

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
1 CrHe128/11 0.2 mL
R1 = 320.31 g/L Chroomzuur
2 CrHe128/11 0.2 mL
3 CrHe128/11 0.2 mL
STATISTICS
Mean value x = 320.32 g/L Chroomzuur
Standard deviation s = 0.22772 g/L Chroomzuur
Method Remarks
Method 02 Chroom(VI)-bep in Cr-baden
Version 03-11-2000 10:58
Title
Method ID . . . . . . . . . . . . . 02
• Cr(VI) is reduced to Cr(III) by the addition of ti-
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+ + Cr3+
Entry type . . . . . . . . . . . . . Fixed volume
Volume [mL] . . . . . . . . . . . 0.2
Molar mass M . . . . . . . . . . . . 99.99
Stir
. . . Manual Chemicals
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
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DM140
mL flask with 10% sulphuric acid and fill to the
Unit of meas. . . . . . . .
.
.
.
.
.
.
mV
to volume
mark with deionized water.
Volume [mL] . . . . . . . . . . . 17
Wait time [s] . . . . . . . . . . 60
∆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 brochure18,
∆E [mV] . . . . . . . . . . . . . 1.0
∆t [s] . . . . . . . . . . . . . 1.0 "Standardization of Titrants", 2000.
t(min) [s] . . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . . 20.0
Recognition
Threshold . . . . . . . . . . . . 300
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No Table of measured values:
Termination
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 . . . . . . . . . . . . . . 19.8000 0.0800 967.2 -20.4 -254.4 5:54
Decimal places . . . . . . . . . . . 0 19.8500 0.0500 960.1 -7.1 -142.2 6:14
Result unit . . . . . . . . . . . . 19.9300 0.0800 866.5 -93.6 -1170.4 6:35
Result name . . . . . . . . . . . .
EQP1 19.9800 0.0500 596.5 -270.0 -5399.8 6:41
Statistics . . . . . . . . . . . . . No
20.0300 0.0500 575.8 -20.7 -413.6 7:12
Calculation
20.0800 0.0500 564.9 -10.9 -218.4 7:15
Formula . . . . . . . . . . . . . .
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
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
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 = 1 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(1/2 AgNO3) = 0.2 mol/L
Standard: Sodium chloride

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
Method
Method 25003 Free CN- in Cu bath
Remarks
Version 17-01-2001 10:50
• The cyanid content determination in e.g. brass
Title
Method ID . . . . . . . . . . . . . 25003
electroplating bath is very important to achieve
Title . . . . . . . . . . . . . Free CN- in Cu bath
Date/time . . . . . . . . . . . . . 17-01-2001 10:50 optimum plating efficiency.
Sample
Sample ID . . . . . . . . . . . . . Cu bath • The method was developed on the DL25 titrator and
Volume [mL] . . . . . . . . . . . 1.0 has been adapted for the DL5x-/DL7x-titrators.
Molar mass M . . . . . . . . . . . . 26.01
.
.
.
.
.
.
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 . . . . . . . . . . . . . 1/2 AgNO3
2) 1 mL aliquot is poured in the titration beaker.
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.2
DP550
3) Add 5 mL 10% potassium iodide solution (KI).
Unit of meas. . . . . . . .
.
.
.
.
.
.
mV
to volume
4) 40 mL deionized water is added to the sample.
Volume [mL] . . . . . . . . . . . 1.5
Wait time [s] . . . . . . . . . . 20
∆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] . . . . . . . . . .
.
.
.
.
.
.
0.5 the reaction between silver and cyanide ion:
∆t [s] . . . . . . . . . . . . . 1.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0
Ag+ + 2 CN- = Ag(CN)2 -
Threshold . . . . . . . . .
.
.
.
.
.
.
200
No
As long as free cyanide is still present, the solu-
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Negative
tion remains clear, but the first excess of silver
Termination
causes formation of a white solid that mark the
at potential . . . . . . . . . . No endpoint:
at slope . . . . . . . . . . . . No
after number EQPs . . . . . . . . Yes Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
n = . . . . . . . . . . . . . 1
Evaluation
. . . No • To obtain a accurate determination of the end-
Procedure . . . . . . . . . . . . Standard point, potassium iodide is used as an indicator.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No During titration, any silver iodide which would
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 . . . . . . . . . . . . . . C=M/z
Decimal places . . . . . . . . . . . 2 lence point is reached:
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . . . . . Sample content AgI + 2 CN- = [Ag(CN)2] - + I-
Statistics . . . . . . . . . . . . . Yes
Calculation • After the equivalence point, the formation of yel-
Formula . . . . . . . . . . . . . . R2=R1*10
Constant . . . . . . . . . . . . . . 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
Sample data . . . . . . . . .
.
.
.
.
.
.
Yes
No Literature
E - V curve . . . . . . . . . . . . Yes
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
.
.
.
.
.
.
Yes
No
• Application note, DL25 Application Brochure
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
.
.
.
.
.
.
No
No
"Petroleum and electroplating", ME-51724627.
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
.
.
.
.
No
No
• Vogel's textbook of quantitative inorganic
analysis, 4th edition, Longman Group Limited ,
1978.
Disposal • D.A. Skoog, D.M. West, "Fundamentals of Ana-
Cyanide waste lytical Chemistry", Holt, Rinehart, and Winston,
1969.
• Application no. M525 in Application brochure18,
Other titrators
DL50 Graphix, DL53/DL58, DL70ES, DL77. Author: R. Böhlen, MT Switzerland
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
Substance: Free cyanide, CN- AT261
M = 26.02, z = 1
Method: 40004
5 mL 20% NaOH (5 mol/L) Accessories: Titration beakers ME-101974
Titrant: Silver nitrate, AgNO3 Indication: DM141

c(1/2 AgNO3) = 0.2 mol/L

Results:
CN- n Comments
Mean value 50.994 g/L 5 DL40 application no. 168
as NaCN, M=49

deviation srel
Method
Method 40004 Free CN- in Zn bath
Remarks
Version 18-01-2001 10:13
Title
Method ID . . . . . . . . . . . . . 40004 and has been adapted for the DL5x- and DL7x-
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Free CN- in Zn bath
. . . 18-01-2001 10:13
titrators.
Sample
Sample ID . . . . . . . . . . . . . Zn bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
1.0
Sample preparation
Molar mass M . . . . . . . . .
.
.
.
.
.
.
26.01
1
1) 1 mL zinc bath are diluted in a titration beaker
.
.
.
.
.
.
Stand 1
Manual
by adding 40 mL deionized water.
Stir
Speed [%] . . . . . . . . . . . . . 50
2) 5 mL 20% NaOH solution are added.
Time [s] . . . . . . . . . . . . . . 10
EQP titration
Titrant/Sensor
Titrant . . . . . . . . . . . . . 1/2 AgNO3
Reaction
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.2
DM141
• The following equation describes the interde-
Unit of meas. . . . . . . .
.
.
.
.
.
.
mV
to volume
pendence of the different ions in a zinc bath:
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 hydroxide is added, then all
∆E [mV] . . . . . . . . . . . . . 0.5
∆t [s] . . . . . . . . . . . . . 1.0 cyanide is set free, and can be precipitated by
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . . . . . 30.0 silver ions Ag+ added during titration:
Recognition
Threshold . . . . . . . . . . . . 300 Ag+ + 2 CN- = [Ag(CN)2] -
Range . . . . . . . . . . . . . . No
Tendency . . . . . . . . .
Termination
. . . Positive
Note that silver forms in a first step the soluble
.
.
.
.
.
.
15.0
No
complex Ag(CN)2- . As long as free cyanide is
at slope . . . . . . . . .
.
.
.
.
.
.
No
Yes
still present, the solution remains clear, but the
n = . . . . . . . . . .
.
.
.
.
.
.
1
No
first excess of silver causes formation of a white
Evaluation
solid that mark the endpoint:
Potential 1 . . . . . . . . . . . No Ag+ + Ag(CN)2- = Ag[Ag(CN)2]
Potential 2 . . . . . . . . . . . No
Condition . . . . . . . . . . neq=0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
• The indication with the DM141 combined silver
Constant . . . . . . . . . . . . . . C=M/z electrode is superior to the traditional turbidi-
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L metric indication with potassium iodide.
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . . . . . R2=Q*C2 • The Zn content analysis is described in M191.
Constant . . . . . . . . . . . . . . C2=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
CN in sample
Yes
LIterature
Calculation
Formula . . . . . . . . . . . . . .
• DL40 application no. 168
Constant . . . . . . . . . . . . . . • Vogel's textbook of quantitative inorganic analy-
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . . . . . sis, 4th ed., Longman Group Limited , 1978.
Result name . . . . . . . . . . . .
Statistics . . . . . . . . . . . . . No • Application no. M525 in Application brochure18,
Report
Output . . . . . . . . . . . . . . . Printer "Standardization of Titrants", 2000.
Results . . . . . . . . . . . . . . No
E-V curve (DL40 application):

All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
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
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
Substance: Zn2+ AT261
M = 65.37, z = 1
Method: 40005
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
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

deviation srel
Method
Method 40005 Zn in Zn bath
Remarks
Version 18-01-2001 10:30
Title
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Zn in Zn bath
. . . 18-01-2001 10:30
titrators.
Sample
Sample ID . . . . . . . . . . . . . Zn bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
1.0
Molar mass M . . . . . . . . .
.
.
.
.
.
.
65.37
1 before starting titration (100% transmission).
Dispense
Titrant . . . . . . . . . . . . . . EDTA Sample preparation
Volume [mL] . . . . . . . . . . . . 6.0
Stir
Speed [%] . . . . . . . . . . . . . 50 1) 1 mL zinc bath are diluted in a titration beaker
Time [s] . . . . . . . . . . .
EQP titration
. . . 20
Titrant/Sensor
Titrant . . . . . . . . . . . . . ZnSO4
2) 5 mL buffer solution pH 10 are added
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DP550
3) 5 mL 37-40% formaldehyde solution are added.
Unit of meas. . . . . . . .
.
.
.
.
.
.
mV
to volume
4) 0.5 mL indicator solution are added before titra-
Volume [mL] . . . . . . . .
Wait time [s] . . . . . . .
.
.
.
.
.
.
2.5
10
tion.
Titrant addition . . . . . . . . . . Incremental
∆V [mL] . . . . . . . . . . . . . 0.02
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
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
No
of an excess of EDTA (6 mL).
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Negative
1. Zn(II) ions form complexes with EDTA:
Termination
at potential . . . . . . . . . . No Zn 2+ + H2-EDTA2- = Zn-EDTA2- + 2 H+
at slope . . . . . . . . . . . . No
n = . . . . . . . . . . . . . 1
comb. termination criteria . . . No 2. EDTA excess is titrated with 0.1 mol/L zinc sul-
Evaluation
Procedure . . . . . . . . . . . . Standard phate solution according to the above reaction.
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Condition . . . . . . . . . . neq=0 3. The colour change of Erio T in alkaline medi-
Calculation
Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m um will be from blue to red when EDTA is titrated
Constant . . . . . . . . . . .
.
.
.
.
.
.
C=M/z
2 with Zn(II).
Result unit . . . . . . . . . . . . g/L
Statistics . . . . . . . . . . . . . Yes
Calculation Chemicals
Formula . . . . . . . . . . . . . . R2=R1*C2
Constant . . . . . . . . . . . . . . C2=M*1000/z
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . mg • Buffer solution pH 10:
Result name . . . . . . . . . . . . Zn in sample
Statistics . . . . . . . . . . . . . Yes 70 g ammonium chloride, NH4Cl, and 570 mL
Calculation
Formula . . . . . . . . . . . . . . ammonium hydroxide, NH4OH, are dissolved
Constant . . . . . . . . . . .
.
.
.
.
.
. 0 in 1000 mL volumetric flask. Diluto to the mark
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
. with deionized water.
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . .
All results . . . . . . . . .
.
.
.
.
.
.
No
Yes
Literature
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . Yes • DL40 application no. 175
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes • Applications no. M528 and 538 in Applica-
∆E/∆V - V curve . . . . . . .
∆2E/∆V2 - V curve . . . . . . .
.
.
.
.
.
.
Yes
No tion brochure18, "Standardization of Titrants",
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
.
.
.
.
.
.
No
No 2000.
V - t curve . . . . . . . . . . . . No
∆V/∆t - t curve . . . . . . . . . . No
Disposal
Zinc is precipitated as zinc hydroxide with NaOH
Other titrators or Ca(OH)2 and then filtrated (precipitate: special
DL50 Graphix, DL55/DL58, DL70ES, DL77. waste).
Authors: U. Büchi / P. Schauwecker

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
Substance: Au3+ AT261
M = 196.97, z = 1
Method: 40005
Adjust to pH 3-5 with HNO3. Accessories: Titration beakers ME-101974
Titrant: Silver nitrate, AgNO3 Indication: DM141

c(AgNO3) = 0.1 mol/L

Results:
Au3+ n Comments
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

deviation srel
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-
Method ID . . . . . . . . . . . . . 40005
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . Zn in Zn bath
. . . 18-01-2001 16:30
titrators.
Sample
Sample ID . . . . . . . . . . . . . Au-solution
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
5.0
Sample preparation
Molar mass M . . . . . . . . . . . . 196.97 1) 5mL standard solution are diluted in a titration
Titration stand . . . . . . . . . . Stand 1 beaker by adding 50 mL deionized water.
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 . . . . . . . . . . . . . AgNO3
Concentration [mol/L] . . . . . . 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
.
.
.
.
.
.
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] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
0.5
2.0 • Gold is precipitated as AgAu(CN)2 during titra-
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
tion with silver nitrate:
Recognition
Threshold . . . . . . . . . . . . 800
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
Ag + + Au(CN)2- = AgAu(CN)2
Termination
.
.
.
.
.
.
10.0
No
Nitric acid is added to increase the steepness of
at slope . . . . . . . . .
.
.
.
.
.
.
No
Yes
the potential jump at the equivalence point.
n = . . . . . . . . . . . . . 1
Evaluation
• If the standard solution should contain chloride,
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 . . . . . . . . . . . . Au content
Statistics . . . . . . . . . . . . . Yes • Gold electroplating baths contain free cyanide.
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ Interference from free cyanide can be avoided
Constant . . . . . . . . . . .
.
.
.
.
.
. 3 by adjusting the pH to 5-6 using 30-40% form-
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Consumption
aldehyde solution. After a waiting time of 15-20
Statistics . . . . . . . . . .
Calculation
. . . Yes
minutes, 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
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 Literature
∆V/∆t - t curve . . . . . . . . . . No
• DL40 application no. 8121, 1982.
Disposal • Vogel's textbook of quantitative inorganic

Special waste. CAUTION: cyanide is toxic! analysis, 4th edition, Longman Group Limited ,
1978.
Other titrators
DL50 Graphix, DL55/DL58, DL70ES, DL77. • Application no. M525 in Application brochure18,
Authors: MT Analytical, Application laboratory
METTLER TOLEDO
M208 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
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 re-
chosen the precipitation method with hydroquinone. gia.
Most of the associated metals do not interfere with the 2. Au3+ is reduced by an excess of hydroquinone:
determination. As the precipitation of gold is too slow to Au precipitates and quinone is formed
execute a direct titration with hydroquinone, an excess
of hydroquinone is added to the dissolved gold. The O
excess is titrated back with cerium sulfate. Three indivi-
dual methods are necessary for the gold determination: pH ~ 1
2 Au3+ + 3 = 2 Au + 6H+ + 3
• The cer method is used for the factor determination 6e -
of cerium sulfate vs. hydroquinone.

O
• The hydr method is used for the standardization of 3. The excess of hydroquinone is then oxidized by
these two titrants with pure gold. cerium sulfate (back titration):
• The gold method is used for the determination of
pure gold or its content in alloys. O
If the gold content is unknown, the test method is pH ~ 1
used. + 2 Ce4+ = + 2 Ce3+ + 2H+
2e-
The following points indicate that these methods are
O
suitable for the gold determination:
• The titration of hydroquinone with cerium sulfate
is reproducible (see cer method). mmol C6H6O2 dispensed (excess)
• 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, 1
/3 Au 3+
VEQ ∗ c(Ce(SO4)2 ∗ t
platinum and palladium do not interfere (Ref. 2).
We have found that also silver does not interfere.
mmol Au =
[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( /2 C6H6O2)
1
= 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
1. A. Chow, The Stability of Gold Solutions, Talanta 18 (1971),
Titration Time of one Sample 453-456.
2. S. C. Soundar Rajan and N. Appala Raju, Titrimetic Determination
Method cer hydr gold test of Gold by Precipitation with Hydroquinone, Talanta 22 (1975),
Time [min] 6 10 10-15 20-25 185-189.
METTLER TOLEDO
M209 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 dis-
solved.
– 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
1/1 C 6H 6O 2 1.5 mL Fixed volume U

R1 = 0.98115 Factor
R1 = 0.98202 Factor
R1 = 0.98217 Factor
R1 = 0.98261 Factor
STATISTICS
Mean value x = 0.98199 Factor
Standard deviation s = 0.000611 Factor
AUXILIARY VALUE
New value H2 = 0.981989 Factor
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
Method ID . . . . . . . . . . . . . cer
precipitation occurs. We recommend to prepare a
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 recom-
Entry type . . . . . . . . . .
.
.
.
.
.
.
Stand 1
Fixed volume U
mend to prepare a new solution every 10 days.
Volume [mL] . . . . . . . . . . . 1.5 mL
ID1 . . . . . . . . . . . . . . . . C 6H 6O 2
Molar mass M . . . . . . . . . . . . 110.11
Equivalent number z . . . . . . . . 2 Calculation
Pump • Fixed volume U of hydroquinone =
Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L
Volume [mL] . . . . . . . . . . . . 40.0 dispensed volume VDISP = 1.5 mL
Dispense
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Concentration . . . . . . . . . . . 0.05
. . . 1.5
Volume [mL] . . . . . . . . .
Stir VDISP * c(1/2 C6H6O2)
Speed [%] . . . . . . . . . . . . . 50 fce/hy =
Time [s] . . . . . . . . . . . . . . 10
Titration VEQ * c(Ce(SO4)2)
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
Titration mode . . . . . . . .
Predespensing 1 . . . . . .
.
.
.
.
.
.
EQP
mL
• If the mean value x of fce/hy is less than 0.9 or greater
Volume [mL] . . . . . . . . . 6.3 than 1.1, then the INSTRUCTION method function
∆E(set) [mV] . . . . . . . . . 8.0 is displayed.
∆V (min) [mL] . . . . . . . 0.01
∆V (max) [mL] . . . . . . . 0.2
Measure mode . . . . . . . . . . EQU • The mean value x 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
Table of measured values

n = . . . . . . . . . . . . . 1
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)
Constant . . . . . . . . . . . . . . ET1 0.0000 432.8 0:30
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

METTLER TOLEDO
M210 Standardization of hydroquinone with pure gold
Sample: Pure gold: 0.023 - 0.026 g Instruments: - METTLER TOLEDO DL70ES/77

- METTLER balance AT261
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
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
RESULTS
1/1 Gold 0.024295 g Weight m
R1 = 4.778 mL
R2 = 0.22028 mmol C 6H 6O 2
R3 = 0.99996 Titer C 6H 6O 2
R1 = 4.842 mL
R2 = 0.21503 mmol C 6H 6O 2
R3 = 0.99924 Titer C 6H 6O 2
R1 = 4.835 mL
R2 = 0.21545 mmol C 6H 6O 2
R3 = 0.99788 Titer C 6H 6O 2
R1 = 4.867 mL
R2 = 0.21285 mmol C 6H 6O 2
R3 = 0.99784 Titer C 6H 6O 2
STATISTICS
Mean value x = 0.99873 Titer C6H6O2
Standard deviation s = 0.001046 Titer C6H6O2
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
Method hydr Titer of C6H6O2, Ce(SO4)2
Version 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 . . . . . . . . . . . . . Weight m
Lower limit [g] . . . . . . . . . 0.023 – Weigh in this sample with a precision of 0.001 mg
Upper limit [g] . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.026
Gold
and put it in the glass beaker.
Molar mass M . . . . . . . . . . . . 196.967 – Add 5 mL conc. HCl and 1.5 mL conc. HNO3 (fume
Temperature sensor . . . . . . . . . Manual hood). Never use prepared aqua regia (unstable!).
Pump
– 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 . . . . . . . . . . . 0.05
Volume [mL] . . . . . . . . . . . . 1.4*H2+304.6*m ultra-sonic bath (room temperature).
Stir
Speed [%] . . . . . . . . . . . . . 50
– Evaporate to almost dryness (color changes from
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 . . . . . . . . . . . . . . Ce(SO4)2
Concentration [mol/L] . . . . . . . 0.01 – Repeat this procedure until no yellow fumes are
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DM140-SC
mV
formed anymore.
Titration mode . . . . . . . . . . . EQP – Let the sample cool to room T, then titrate.
Predespensing 1 . . . . . . . . . mL
Volume [mL] . . . . . . . . . 0.9*R
∆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 . . . . . . . . . . . . C 6H 6O 2 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
Ri (i=index) . . . . . . . . . . . . 3
E-V curve
Outlier test . . . . . . . . . . . . Yes
Titer
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Formula t = . . . . . . . x
Titer
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Formula t = . . . . . . . x*H2
Record
All results . . . . . . . . . . . . Yes
Table of values . . . . . .
E - V curve . . . . . . . .
.
.
.
.
.
.
.
.
Yes
Yes
Other titrators
Auxiliary value DL70ES, DL77.
ID text . . . . . . . . . . . . . . Titer of C6H6O2
Formula . . . . . . . . . . . . . . H3=x
Disposal
Authors: MT Analytical, Application laboratory Special waste.
Remarks c. Titer determination of C6H6O2 vs. gold
Calculations
thy = z * m * 1000
M (VDISP * c(1/2 C6H6O2) – VEQ * c(Ce(SO4)2) * fce/hy)
a. Dispensing of hydroquinone
An excess of hydroquinone is dispensed depending
on the size of the gold sample. Furthermore, ap- The titer of C6H6O2 thy is stored as auxiliary value H3
prox. 7 mL of the cerium sulfate titrant should be for further use in the "gold" method.
consumed by the back titration. Thus the dispensed
volume of hydro-quinone (VDISP) is calculated in
the DISPENSE function.
d. Titer determination of Ce(SO4)2 vs. gold
VDISP = mL hydroquinone + mL hydroquinone The factor fce/hy was obtained by the standardizati-
reacted with gold back titrated with Ce(SO4)2 on of cerium sulfate with hydroquinone (method
"cer"). The titer of cerium sulfate must be referred
z * m * 1000 7 mL * c(Ce(SO4)2) * fce/hy
= + to gold.
M * c(1/2 C6H6O2) c(1/2 C6H6O2)
tce = thy * fce/hy = thy * H2
= 304.6 * m + 1.4 * H2
The best accuracy is achieved if the consumption

of hydroquinone and cerium sulfate is less than where
1 burette volume each, i.e. 10 mL. Therefore the
VDISP = dispensed volume of hydroquinone
sample weight must lie in the range of 0.023 and
[mL]
0.026 g gold. Also the titer values of both titrants
must lie in the range of 0.95 and 1.1. VEQ = cerium sulfate consumption by back
titration
VEQth = calculated cerium sulfate consumption
for back titration
b. Predispensing of cerium sulfate (back titration) z= equivalent number of gold = 3
Predispensing is always applied to speed up the m= size of gold sample [g]
titration. Here a predispensing volume of 90% of
M= molar mass of gold = 196.967
the total cerium sulfate consumption (VEQth) is
used. This volume is calculated in the first CAL- c( /2 C6H6O2)= hydroquinone concentration =
1
CULATION function. 0.05 mol/L

c(Ce(SO4)2 = cerium sulfate concentration =
VDISP c(1/2 C6H6O2) z * m * 1000
VEQth = * – 0.01 mol/L
fce/hy c(Ce(SO4)2) M * c(Ce(SO4)2) * fce/hy
fce/hy = factor of cerium sulfate vs. hydroquinone
(stored as H2)
VEQth = VDISP/H2 * 5 – m * 1523 * H2
Reaction Time
The complete reduction of gold with hydroquinone
takes about 2 minutes; thus the stirring time shall not
be less than 180 s.
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 - Pump ME-65241
- Ultrasonic bath
Titrant 1: Hydroquinone
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
Method gold Purity of gold samples 08-April-1993 8:48

User
RESULTS

R1 = 38.044 % purity
R2 = 9.131 carat purity
R1 = 38.070 % purity
R1 = 38.108 % purity
R1 = 38.010 % purity
STATISTICS
Mean value x = 38.058 % purity
Standard deviation s = 0.041247 % purity
STATISTICS
Mean value x = 9.134 carat purity
Standard deviation s = 0.009899 carat purity
AUXILIARY VALUE
New VALUE H4 = 0.375
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
Title
Method ID . . . . . . . . . . . . . gold value H1. If the gold content is unknown, use the
Title . . . . . . . . . . .
Date/time . . . . . . . . .
. . . . Purity of gold samples
. . . . 08-April-1993 8:48
"test" method (see M180). Enter thy as H3.
Sample • The gold concentration of the sample entered as
Number samples . . . . . . . . . . . 4
Titration stand . . . . . . . . . . Stand 1 carat or percent is automatically transformed into
Entry type . . . . . . . . .
Lower limit [g] . . . . .
.
.
.
.
.
.
.
.
Weight m
0.02
the fraction of gold and stored as H4 using the
Upper limit [g] . . . . . . . . . 0.08 AUXILIARY VALUE functions.
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . . . . . . 196.967
.
.
.
.
.
.
.
.
3
Manual
Sample Preparation
Auxiliary value
ID text . . . . . . . . . . . . . .
Proceed with the sample preparation as described in
Formula . . . . . . . . . . . . . . H4=H1/24 method "hydr". The following remarks are impor-
Condition . . . . . . . . . . . . . Yes
Condition . . . . . . . . . . . . H1<=24 tant:
Auxiliary value
ID text . . . . . . . . . . . . . . • Press alloys as thin as possible using a rolling device
Formula . . . . . . . . . . . . . . H4=H1/100
Condition . . . . . . . . . . . . . Yes so that the dissolution is easier.
Condition . . . . . . . . . . . . (H1>24)!(H1<=100)
Pump • Use an ultrasonic bath especially for silver alloys,
Auxiliary reagent . . . . .
Volume [mL] . . . . . . . .
. . . . HCl 0.1 mol/L
. . . . 40.0
be-cause silver chloride does passivate the gold
Dispense surface.
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Concentration . . . . . . .
Volume [mL] . . . . . . . .
. . . . 0.05
. . . . 1.2*H2+304.6*m*H4/H3
• Evaporate the aqua regia solution.
Stir
Speed [%] . . . . . . . . . . . . . 50
• Add 5 mL conc. HCl to the beaker and put it in the
Time [s] . . . . . . . . . . . . . . 180 ultrasonic bath for 5 minutes.
Titration
Titrant . . . . . . . . . . . . . . Ce(SO4)2 • Evaporate again.
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DM-140-SC
mV
• If it is not yet dissolved, repeat the procedure.
Predespensing 1 . . . . .
.
.
.
.
.
.
.
.
EQP
mL
• Never evaporate to complete dryness!
Volume [mL] . . . . . . . . . 2.1
∆E(set) [mV] . . . . . . . . . 8.0 Sample Weight (g)
∆V (min) [mL] . . . . . . . 0.02
∆V (max) [mL] . . . . . . . 0.2 Content (carat) lower limit upper limit
Measure mode . . . . . . . . . . EQU
∆E [mV] . . . . . . . . . . . 0.5 24 0.023 0.026
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0 21 0.026 0.030
t(max) [s] . . . . . . . . . . 30.0
Threshold . . . . . . . . . . . . 400.0 18 0.031 0.034
EQP range . . . . . . . . . . . . Yes
Limit A . . . . . . . . . . . 500
14 0.040 0.044
Limit B . . . . . . . . . . . 700 12 0.046 0.052
n = . . . . . . . . . . . . . 1
9 0.062 0.069
Calculation
Result name . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
purity
R=100*(QDISP-Q)*C
Dispensing of Hydroquinone
Constant . . . . . . . . . . . . . . C=M/(m*z*1000)
Result unit . . . . . . . . . . . . %
Decimal places . . . . . . . . . . . 3 • An excess of hydroquinone is dispensed depending
Calculation
Result name . . . . . . . . . . . . purity on the sample size and the gold concentration.
Formula . . . . . . . . . .
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
R2=24*(QDISP-Q)*C2
C2=M/(m*z*1000)
• Furthermore, the dispensed volume (VDISP) is
Result unit . . . . . . . . . . . . carat calculated for a consumption of 6 mL cerium sulfate
Decimal places . . . . . . . . . . . 3
Statistics
Ri (i=index) . . . . . . . . . . . . R1 VDISP =
Outlier test . . . . . . . . . . . . Yes = mL hydroquinone + mL hydroquinone back
Statistics
Ri (i=index) . . . . . . . . . . . . R2
reacted with gold titrated with Ce(SO4)2
Rel. standard deviation srel . . . . Yes z * m * Aux * 1000 6 mL * c(Ce(SO4)2) * fce/hy
Outlier test . . . . . . . . . . . . Yes = +
Record M * c(1/2 C6H6O2) * thy c(1/2 C6H6O2)
All results . . . . . . . . . . . . Yes
= 304.6 * m * H4/H3 + 1.2 * H2
Calculation of the result Reaction Time
• The complete reduction of gold with hydroquinone

The gold content Au is:
takes about 3 minutes; thus the stirring time shall
not be less than 180 s.
Au = 24 * M * (QDISP – Q) [carat]
z * 1000 * m
Titration Parameters
where • The titration curve may show noisy behavior in the

VDISP = dispensed volume of hydroquinone range of the equivalence point. This may especially
[mL] occur with samples of low gold content. In this case
QDISP = dispensed amount of hydroquinone we recommend to increase the minimum increment
[mmol] ∆V(min) to >0.02 mL.
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( /2 C6H6O2) = hydroquinone concentration =
1
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
Disposal
Special waste.
Other titrators
DL70ES, DL77. Authors: MT Analytical, Application laboratory
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
Title
Method ID . . . . . . . . . . . . . test hydroqui-none is done by a titration in order
Title . . . . . . . . . . .
tent
. . . . Approximate gold con-
• to determine the total amount of C6H6O2 dispensed
Date/time . . . . . . . . .
Sample
. . . . 10-April-1993 11:09
and
.
.
.
.
.
.
.
.
1
Stand 1 • to obtain an excess of at least 1 mL C6H6O2 (titrant
Lower limit [g] . . . . . . . . . 0.03 addi-tion ∆V = 0.5 mL).
Upper limit [g] . . . . . . . . . 0.06
ID1 . . . . . . . . . . . . . . . . Gold
Molar mass M . . . . . . . .
.
.
.
.
.
.
.
.
196.967
3
Titration Curve: Gold Reduction with Hydroquinone
Pump
Volume [mL] . . . . . . . . . . . . 40.0
Stir
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10
Titration
Titrant . . . . . . . . . . . . . . 1/2 C6H6O2
Sensor . . . . . . . . . . . . . . . DM-140-SC
Unit of meas. . . . . . . . . . . . mV
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
Termination after n EQPs . . . . Yes The total amount of C6H6O2 dispensed is stored as
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard auxiliary value H5.
Auxiliary value
ID text . . . . . . . . . . . . . . Amount of C6H6O2
Formula . . . . . . . . . . . . . . H5=Q+QEX 2nd TITRATION function: The excess of hydroquinone
Stir
Speed [%] . . . . . . . . . . . . . 50 is titrated back with cerium sulfate.
Time [s] . . . . . . . . . . . . . . 120
Titration
Titrant . . . . . . . . . . . . . . Ce(SO4)2
Sensor . . . . . . . . . . .
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
DM-140-SC
mV
Titration Curve: Back Titration with Cerium Sulfate
∆E(set) [mV] . . . . . . . . . 8.0
∆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
n = . . . . . . . . . . . . . 1
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 . . . . . . . .
Formula . . . . . . . . . .
.
.
.
.
.
.
.
.
content
R2=24*(H5-Q[2])*C2
Disposal
Constant . . . . . . . . . .
Result unit . . . . . . . .
.
.
.
.
.
.
.
.
C2=M/(m*z*1000)
carat
Special waste.
Decimal places . . . . . . . . . . . 1
Record
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
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

Results:
PbO2 n Comments
Mean value 8.5547 % 5 DL40 application no. 305
Theoretical 8-10 % Sample size: 1 g

content
Consumption: 20 mL

deviation srel
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
Method Remarks
Method 40006 PbO2
Method ID . . . . . . . . . . . . . 40006
Title . . . . . . . . . . . . . PbO2 titrators.
Date/time . . . . . . . . . . . . . 19-01-2001 17:32
Sample
Sample ID . . . . . . . . . . . . . Lead in batteries
• The Pb(IV) content is expressed as PbO2 and is
Entry type . . . . . . . . . . . . . Weight detemined by back titration after addition of excess
Lower limit [g] . . . . . . . . . 0.5
Upper limit [g] . . . . . . . . . 1.5 hydrogen peroxide solution.
Molar mass M . . . . . . . . . . . . 239.2
Stir
. . . Manual Sample preparation
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
Sensor . . . . . . . . . . . . . DM140 solution until all red traces are dissolved.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No 2) 5 mL 10% hydrogen peroxide solution are added
∆E(set) [mV] . . . . . . . . . . 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:
∆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
No
Pb4+ + 2 e- = Pb2+
Range . . . . . . . . . . . . . . No
Termination 3) 30 mL hot deionized water are added and stir to
at potential . . . . . . . . . . No achieve complete solvation.
at slope . . . . . . . . . . . . No
n = . . . . . . . . . . . . . 1
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
.
.
.
.
.
.
Standard
No
Procedure
Potential 2 . . . . . . . . . . . No
Stop for reevaluation . . . . . . Yes 1) The exact concentration of the H2O2-solution is
Condition . . . . . . . . . . neq=0
Calculation determined by performing a blank titration using
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R=(H4-Q)*C/m
C=M/(10*z) a similar method as for the sample determination.
Result unit . . . . . . . . .
.
.
.
.
.
.
4
% The blank value is stored as auxiliary value H4
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Pb content
Yes
(mmol).
Calculation
Formula . . . . . . . . . . . . . . R2=VEQ
2) Pb(IV) is then determined by a back-titration of
Constant . . . . . . . . . . .
.
.
.
.
.
. 3
excess H2O2 using potassium permanganate as a
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Consumption
titrant:
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
2MnO4 - + 5 Η2Ο2 + 6 H+ =
Decimal places . . . . . . . . . . . 0
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
2Mn2+ + 5O2 + 8Η2O (z =2)
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . .
.
.
.
.
.
.
No
Yes
Literature
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes • DL40 application no. 305
∆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: MT Analytical, Application laboratory
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
Results:
Pb2+ n Comments
Consumption: 1.7 mL

deviation srel
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
Method Remarks
Method 40007 Pb2+
Title
Method ID . . . . . . . . . . . . . 40007
and has been adapted for the DL5x- and DL7x-
Title . . . . . . . . . . . . . Pb2+ titrators.
Date/time . . . . . . . . . . . . . 22-01-2001 10:47
Sample
Sample ID . . . . . . . . . . . . . Pb/Sn/Sb alloy
• The Pb(II) content is detemined by complexometric
Entry type . . . . . . .
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
Fixed volume
10.0
titration with EDTA.
Molar mass M . . . . . . . . . . . . 207.2
Titration stand . . . .
Pump . . . . . . . .
.
.
.
.
.
.
.
.
.
.
.
.
ST20A
No
Sample preparation
Rinse . . . . . . . . . . . . . . Yes
Solvent . . . . . . . . . . . H 2O
Volume . . . . .
Conditioning . . . .
.
.
.
.
.
.
.
.
.
.
.
.
20.0
No
1) Dissolve 1-1.5 g of the finely pulverized alloy in a
Temperature sensor . . .
Stir
. . . . . . Manual 250 mL beaker.
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.
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 solu-
∆V [mL] . . . . . . . . . . . . . 0.05 tion.
Measure mode . . . . . . . . . . . . Equilibrium controlled 5) Boil 2 minutes.
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
0.5
2.0 6) Cool to room temperature.
t(min) [s] . . . . . . . .
t(max) [s] . . . . . . . .
.
.
.
.
.
.
5.0
30.0
7) Add 5 drops of 0.2% aqueous solution of xylenol
Recognition
Threshold . . . . . . . . . . . . 300
orange and 30% hexamethylene tetramine until the
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
solution turns red (for this sample size you need
Tendency . . . . . . . . .
Termination
. . . Positive about 35 mL).
at maximum volume [mL] . . . . . 5.0 8) Dilute to 200 mL with 1:1 HCl.
at potential . . . . . . . . . . No
at slope . . . . . . . . . . . . No 9) Take aliquots of 10 mL.
n = . . . . . . . . . . . . . 1
Evaluation
Procedure
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No 1) This procedure is only suitable for the determina-
Condition . . . . . . . . . . neq=0 tion of Pb in Pb/Sn/Sb alloy. The alloy is dissolved
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m due to the formation in a strong acid medium of a
Constant . . . . . . . . . . .
.
.
.
.
.
.
C=M/(10*z)
2 soluble chloro-plumbate complex.
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
%
Pb content 2) The solution is diluted to volume using 1:1 HCl
Statistics . . . . . . . . . .
Calculation
. . . Yes
since no precipitate is formed at high concentration
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=VEQ of HCl.
Result unit . . . . . . . . .
.
.
.
.
.
.
3
mL
3) Sn and Sb are masked by tartaric acid. Pb can be
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
Consumption
Yes
directly determined by titration with EDTA:
Calculation
Formula . . . . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
. 0
Pb2+ + H2-EDTA2- = Pb-EDTA2- + 2 H+
Result unit . . . . . . . . . . . .
Result name . . . . . . . . . . . . The colour change at the equivalence point turns
Statistics . . . . . . . . . . . . . No
Report from red to yellow.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . . . . . Yes Literature
∆E/∆V - V curve . . . . . . . . . . Yes
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . . . . . No • DL40 application no. 406
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
METTLER TOLEDO
M194 Determination of nickel in an electroplating bath
Sample: Nickel bath, 0.5 mL Instruments: METTLER TOLEDO DL70

Substance: Nickel as NiSO4, METTLER TOLEDO AT261
M = 262.7 g/mol, z = 1 Matrix Printer Epson LX800
Preparation: Deionised water, 50 mL
Buffer pH 10, 10 mL Method: vd01
0.5 g Murexide/NaCl 1:200 tritu-
ration. 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
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
Mean value x = 82.39 g/L NiSO4.6H2O
Standard deviation s = 0.225 g/L NiSO4.6H2O
Method Remarks
Method vd01 Nickel in Galvanic Bath
Version 13-Sep-1991 15:22 • The Ni(II) content is detemined by complexometric
Title titration with EDTA. Murexide is used as indicator,
Method ID . . . . . . . . .
Title . . . . . . . . .
. . . . vd01
. . . . Nickel in Galvanic Bath and the colour change is monitored by a DP550
Date/time . . . . . . . . .
Sample
. . . . 13-Sep-1991 15:22
phototrode.
Number samples . . . . . . . . . . 8
Titration stand . . . . . . . . . . ST20
Volume [mL] . . . . . . . . . . . 0.5 Sample preparation
ID1 . . . . . . . . . . . . . . . .
Molar mass M . . . . . . . . . . . . 262.7 1) Add the mureide indicator to the sample
Pump
. . . . 1
2) The addition of water and buffer is performed au-
Volume [mL] . . . . . . . .
. . . . H 2O
. . . . 10.0
tomatically by two peristaltic pumps.
Pump
Auxiliary reagent . . . . . . . . . Buffer 10
Volume [mL] . . . . . . . .
Stir
. . . . 10.0 Procedure
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 • Nickel ions forms a yellow complex with murexide
Titration
Titrant . . . . . . . . . . . . . . EDTA in alkaline solution:
Sensor . . . . . . . . . .
Unit of meas . . . . . . . .
.
.
.
.
.
.
.
.
DP550
As installed Ni 2+ + Murexide - → Ni-Murexid+
Predispensing 1 . . . . . . . . . mL Ni forms a more stable complex with EDTA:
Volume [mL] . . . . . . . . . 0.5
∆E(set)[mV] . . . . . . . . . 8.0 Ni-Murexid+ + EDTA 4- → Ni-EDTA2-+ Murex-
Limits ∆V . . . . . .
∆V(min) . . . . . .
.
.
.
.
.
.
.
.
Absolute
0.02 ide-
∆V(max) . . . . . . . . . . 0.1
∆E [mV] . . . . . . .
.
.
.
.
.
.
.
.
EQU
1.0
At the equivalence point, Ni(II) has been com-
∆t [s] . . . . . . . . . . . 1.0 plexed by EDTA and murexide is free in the alka-
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . . . . . . 30.0 line solution. There is a colour change from yellow
Threshold . . . . . . . . . . . 10.0
Maximum volume [mL] . . . . . . . 15.0 to blue-violet.
n = . . . . . . . . .
.
.
.
.
.
.
.
.
1
Standard
• The shape of the titration curve is somewhat af-
Calculation
Result name . . . . . . . . . . . . NiSO4.6H2O
fected by the concentration of the indicator. The
Formula . . . . . . . . . . . . . . R=Q*C/U results, however, do not differ significantly.
Constant . . . . . . . . . . . . . . C=M/z
Result unit . . . . . . . . . . . . g/L
Decimal places . . . . . . . . . . . 2 Chemicals
Rinse
Volume [mL] . . . . . . . .
. . . . H 2O
. . . . 10.0
• Buffer solution pH 10: 570 mL 25% NH3 and
Statistics
Ri (i=index) . . . . . . . .
Standard deviation s . . . .
. . . . R1
. . . . Yes Table of mesured values and E-V curve
Record
Short-form method . . . . . . . . . Yes
All results . . . . . . . . . . . . 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
Other titrators
DL50 Graphix, DL53/55 (use standard methods)
DL58, DL77. Author: J. v.d. Ouweland, MT-NL
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

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
Mean value x = 94.9922 % Silver
Standard deviation s = 0.01715 % Silver
Method Remarks
Method AgO2 Purity of AgNO3 Sample Preparation
Version 23-04-1990 10:51
Title
– Clean the sample with acetone and let it dry – use
Method ID . . . . . . . . . . . . . AgO2 tweezers.
Title . . . . . . . . . . . . . . . Purity of AgNO3
Date/time . . . . . . . . . . . . . 23-04-1990 10:51 – Weigh in a sample corresponding to approx. 40 mg
Sample
Number samples . . . . . . . . . . . 3
Ag and read to ±0.01 mg; then put it in the beaker.
Titration stand . . . . . . . . . . Stand 1 – Add 3 mL of 33% HNO3 and warm up to 60 °C in
Lower limit [g] . . . . . . . . . 0.03 a wa-ter bath until the sample is completely dissol-
Upper limit [g] . . . . .
ID1 . . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.07
Ag Alloy
ved.
Molar mass M . . . . . . . . . . . . 107.868 – Let the sample cool down to room temperature and
Stir add 50 mL deion. H2O.
Speed [%] . . . . . . . . . . . . . 60
Time [s] . . . . . . . . . . . . . . 5 This procedure is prerequisite to achieve high precisi-
Titration
Titrant . . . . . . . . . . . . . . NaCl on.
Sensor . . . . . . . . . . . . . . . DM-141-SC
Unit of meas. . . . . . . . . . . . mV High Precision
Predispensing 1 . . . . . . . . . % nominal content Method and preparation are designed for highest preci-
Metered amount [%] . . . . . . 95.0
Nominal content [%] . . . . . 95.0 sion, i.e. RSD better than 0.050%. Our example shows
Conversion const. . . . . . . M/(10*z)
Titrant addition . . . . . . . . INC a reproducibility of 0.018% RSD. This high precision is
∆V [mL] . . . . . . .
.
.
.
.
.
.
.
.
0.05
EQU
required, for example, by mint companies or electronic
∆E [mV] . . . . . . . . . . . 0.5 circuitry manufacturers.
∆t [s] . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . 3.0
t(max) [s] . . . . . .
Threshold . . . . . . . .
.
.
.
.
.
.
.
.
15.0
500.0
High Speed
.
.
.
.
.
.
.
.
10.0
Yes
The method was also streamlined to fast titrations.
n = . . . . . . . . . . . . . 1
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
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
METTLER TOLEDO
M196 Determination of free potassium cyanide in a silver bath
Sample: Copper bath, 1 mL Instruments: METTLER TOLEDO DL67

Substance: Potassium cyanide, KCN Matrix printer Epson LX800
M = 65.12, z = 1 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
(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

R1 = 110.34 g/L KCN
R2 = 8.49 mL Verbrauch
R1 = 111.64 g/L KCN
R1 = 114.09 g/L KCN
STATISTICS
Mean value x = 112.02 g/L KCN
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
Sample no. . . . . . . . . . . . . . 20
ized water
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
.
.
.
.
.
.
.
.
1.0
Reaction
Molar mass M . . . . . . . . . . . . 65.12
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
Sensor . . . . . . . . . . .
.
.
.
.
.
.
.
.
0.1
DM141-SC
Ag+ + 2 CN- = Ag(CN)2 -
Unit of meas. . . . . . . . . . . . mV
Volume [mL] . . . . .
.
.
.
.
.
.
.
.
to volume
1
As long as free cyanide is still present, the solu-
∆E(set) [mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0
tion remains clear, but the first excess of silver
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
Termination after n EQPs . . . . Yes • since 1 mol of Ag ions reacts with two moles of
n = . . . . . . . . . . . . . 1
Evaluation procedure . . . . . . Standard cyanides, the factor 2 is taken into account in
Rinse
Auxiliary reagent . . . . . . . . . H 2O the calculation.
Volume [mL] . . . . . . . . . . . . 10.0
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
Constant . . . . . . . . . . . . . . C=M*2
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . .
Result name . . . . . . . .
.
.
.
.
.
.
.
.
g/L
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
All results . . . . . . . . . . . . Yes
Literature
• Application note, DL25 Application Brochure
"Petroleum and electroplating", ME-51724627.
• Vogel's textbook of quantitative inorganic
analysis, 4th edition, Longman Group Limited ,
1978.
• D.A. Skoog, D.M. West, "Fundamentals of Ana-
Disposal lytical Chemistry", Holt, Rinehart, and Winston,
Cyanide waste 1969.
Other titrators
DL50 Graphix, DL53/DL55/DL58, DL70ES, DL77. Author: Application laboratory, MT Germany
METTLER TOLEDO
M197 Titration of Tin(II) in acidic tin bath
Sample: Acidic tin bath, 2 mL Instruments: METTLER TOLEDO DL67

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

R1 = 21.34 g/L
R1 = 17.79 g/L
R1 = 17.59 g/L
STATISTICS
Mean value x = 18.91 g/L
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.
Volume [mL] . . . . . . .
Sample ID . . . . . . . . .
.
.
.
.
.
.
.
.
2.0
Reaction
Molar mass M . . . . . . . . . . . . 118.71
Stir
. . . . Manual
• Stannous tin Sn(II) is converted quantitatively
Speed [%] . . . . . . . . . . . . . 50
Time [s] . . . . . . . . . . . . . . 10 into stannic tin Sn(IV) by titration with iodine
EQP titration
Titrant . . . . . . . . . . . . . . 1/2 I2 in the presence of hydrochloric acid:
Sensor . . . . . . . . . . . . . . . DM140-SC
Unit of meas. . . . . . . .
.
.
.
.
.
.
.
.
mV
EQP
SnCl2 + 2HCl + I2 = SnCl4 + 2 HI
Predispensing 1 . . . . . . . . . to volume
Volume [mL] . . . . . . . . . 0
∆E(set) [mV] . . . . .
.
.
.
.
.
.
.
.
DYN
8.0
where
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 + 2e =
-
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
.
.
.
.
.
.
.
.
50.0
Yes
is reduced to iodide.
n = . . . . . . . . .
.
.
.
.
.
.
.
.
1
Standard
• Hydrochloric acid must be present in order to
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m
supply chloride ions for the oxidation, otherwise
Constant . . . . . . . . . .
.
.
.
.
.
.
.
.
C=M/z
2
the readily hydrolysed Sn(SO4)2 is produced. If
Result unit . . . . . . . .
Result name . . . . . . . .
.
.
.
.
.
.
.
.
g/L
Sn2+
necessary, add 5 mL concentrated HCl.
Statistics . . . . . . . . . . . . . Yes
Rinse
Volume [mL] . . . . . . . . . . . . 10.0
Statistik
Ri (i=Index) . . . . . . . . . . . . R1
Record
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
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
50 mL buffer pH 4.5 Accessories: Titration beakers ME-101974
30 mg Xylenol orange
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

deviation srel
Method
Method 40008 ZnSO4 in spin-bath
Remarks
Version 24-01-2001 11:15
Title
Title . . . . . . . . . .
Date/time . . . . . . . . . .
. . . ZnSO4 in spin-bath
. . . 24-01-2001 11:15
titrators.
Sample
Sample ID . . . . . . . . . . . . . Spin bath
Entry type . . . . . . . . . .
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Fixed volume
5.0
Molar mass M . . . . . . . . .
.
.
.
.
.
.
161.4
1 before starting titration (100% transmission).
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
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DP550
Unit of meas. . . . . . . .
.
.
.
.
.
.
mV
No
2) 50 mL buffer solution pH 4.5 are added
∆V [mL] . . . . . . . . . .
.
.
.
.
.
.
Incremental
0.1
3) 30 mg Xylenol orange are added to the sample
Measure mode . . . . . . . . .
∆E [mV] . . . . . . . . . .
.
.
.
.
.
.
1.0
solution.
∆t [s] . . . . . . . . . . . . . 2.0
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . .
Recognition
. . . 30.0
Reaction
Threshold . . . . . . . . . . . . 200
Range . . . . . . . . . . .
Tendency . . . . . . . . .
.
.
.
.
.
.
No
Positive • Zinc ions form a red complex with xylenol orange
Termination
in acidic solution:
at potential . . . . . . . . . . No
at slope . . . . . . . . .
.
.
.
.
.
.
No
Yes
Zn2+ + Xylenol 2- → Zn-Xylenol
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
Formula . . . . . . . . . . . . . . R=Q*C/m
At the equivalence point, all Zn ions have been
Constant . . . . . . . . . . .
.
.
.
.
.
.
C=M/z
4
complexed by EDTA and xylenol orange is free in
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 acetat-
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption eare dissolved in a 1 L volumetric flask. Dilute
Statistics . . . . . . . . . . . . . No
Report to the mark with deionized water.
Output . . . . . . . . . . . . . . . Printer
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . .
.
.
.
.
.
.
No
Yes
Literature
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
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
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

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
Method Remarks
Method 40009 SO42- in spin-bath
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . 40009
. . . SO42- in spin-bath titrators.
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] . . . . . . . . . . . 1.0
Molar mass M . . . . . . . . . . . . 96.01 before starting titration (100% transmission).
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 . . . . . . . . . .
.
.
.
.
.
.
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
Volume [mL] . . . . . . . .
.
.
.
.
.
.
Yes
3.0
beaker.
Wait [s] . . . . . . . . .
.
.
.
.
.
.
20
Incremental
3) 20 mL deionized water are added.
∆V [mL] . . . . . . . . . .
Measure mode . . . . . . . . .
.
.
.
.
.
.
0.1
4) Add 30 mL acetone.
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
2.0
10.0
Steps 3+4: The aqueous mixture is prepared in ad-
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.
n = . . . . . . . . . . . . . 1
Evaluation Reaction
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 . . . . . . . . . . .
.
.
.
.
.
.
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 indicator
Calculation
Formula . . . . . . . . . . . . . . R2=Q*100
is added to the sample solution.
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 2
Result unit . . . . . . . . . . . . g/L
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
SO42- bath
Yes
Chemicals
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ
Constant . . . . . . . . . . .
.
.
.
.
.
. 4
• Mixed indicator:
Result unit . . . . . . . . .
Result name . . . . . . . . .
.
.
.
.
.
.
mL
Consumption
In a 50 mL volumetric flask 0.12 mL 1.6% methy-
Statistics . . . . . . . . . . . . . No lene blue solution and 50 mg Thorin are dissolved
Report
Output . . . . . . . . . . . . . . . Printer in 5 mL 0.1 mol/L hydrochloric acid. Fill up to the
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes mark with deionized water.
Raw results . . . . . . . . . . . . No
Sample data . . . . . . . . . . . . No
E - V curve . . . . . . . . .
∆E/∆V - V curve . . . . . . .
.
.
.
.
.
.
Yes
Yes Literature
∆2E/∆V2 - V curve . . . . . . . . . . No
log ∆E/∆V - V curve . . . . .
E - t curve . . . . . . . . .
.
.
.
.
.
.
No
No
• DL40 application note no. 84-22
V - t curve . . . . . . . . .
∆V/∆t - t curve . . . . . . .
.
.
.
.
.
.
No
No
• DL40 application no. 106
• 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
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 = 1 with serial inteface 8148
AT261
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

deviation srel
Method Remarks
Method 40010 F- soldering salts
Method ID . . . . . . . . . . . . . 40010
Title . . . . . . . . . . . . . F- soldering salts titrators.
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 . . . . . . . . 1 1) Approx. 1 g soldering salts are dissolved in 150 mL
Temperature sensor . . . . . . . . . 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 . . . . . . . . . . . . . 1/3 La(NO3)3
3) After cooling to room temperature, 10 mL buffer
Sensor . . . . . . . . . .
.
.
.
.
.
.
0.1
DX219 pH 6 are added before titration.
Unit of meas. . . . . . . . . . . mV
Predispensing . . . . . . . . . . . No
∆V [mL] . . . . . . . . . .
.
.
.
.
.
.
Incremental
0.2 Reaction
∆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
Range . . . . . . . . . . .
.
.
.
.
.
.
No
No
3 F- + La3+ = LaF3
Termination • 1 mol of La3+ ions reacts with 3 mol of fluoride
at slope . . . . . . . . .
.
.
.
.
.
.
No
No
ions
n = . . . . . . . . . . . . . 1
Evaluation
Procedure . . . . . . . . . . . . Standard Chemicals
Potential 1 . . . . . . . . . . . No
Potential 2 . . . . . . . . . . . No
Condition . . . . . . . . . . neq=0 • Buffer pH 6 solution:
Calculation
Formula . . . . . . . . . . . . . . R=Q*C/m Dissolve approx. 85 g sodium acetate in 1 L deion-
Constant . . . . . . . . . . . . . . C=M/(10*z)
Decimal places . . . . . . . . . . . 2 ized water. While monitoring the pH value, slowly
Result unit . . . . . . . . . . . . %
Result name . . . . . . . . . . . . % F- add glacial acetic acid to achieve pH 6.
Statistics . . . . . . . . . . . . . Yes
Calculation
Formula . . . . . . . . . . .
Constant . . . . . . . . . . .
.
.
.
.
.
.
R2=Q*C2
C2=M*1000/z • Titrant solution :
Result unit . . . . . . . . .
.
.
.
.
.
.
2
mg
Dissolve 14.44 g La(NO3)3 • 6H2O in a 1 L volu-
Result name . . . . . . . . .
Statistics . . . . . . . . . .
.
.
.
.
.
.
F- sample
Yes
metric flask and fill up to the mark to obtain the
Calculation
Formula . . . . . . . . . . . . . . R3=VEQ
concentration c( 1/3 La(NO3)3 ) = 0.1 mol/L.
Constant . . . . . . . . . . . . . .
Decimal places . . . . . . . . . . . 4
Result unit . . . . . . . . . . . . mL
Result name . . . . . . . . . . . . Consumption Literature
Statistics . . . . . . . . . . . . . No
Report
Output . . . . . . . . . . . . . . . Printer • DL40 application note no. 8317
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes
Raw results . . . . . . . . . . . . No
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
METTLER TOLEDO
M201 Standardization of 1/2 Pb(NO3)2
Sample: NaF 0.1 mol/L standard solution, Instruments: METTLER TOLEDO DL53
5 mL Matrix printer Epson LX800
Substance: F - , M = 18.998, z = 1 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

deviation srel
Method Remarks
Method 40011
Version
Titer Pb(NO3)2
26-01-2001 10:12
Title
and has been adapted for the DL5x- and DL7x-
Method ID . . . . . . . . . .
Title . . . . . . . . . .
. . . 40011
. . . Titer Pb(NO3)2
titrators.
Date/time . . . . . . . . . . . . . 24-01-2001 16:30
Sample
Sample ID . . . . . . . . . .
Entry type . . . . . . . . . .
.
.
.
.
.
.
NaF 0.1 M
Fixed volume
Sample preparation
Volume [mL] . . . . . . . . . . . 5
Molar mass M . . . . . . . . . . . . 18.998
.
.
.
.
.
.
1
Stand 1
1) The standard solution is prepared by dissolving
Stir
. . . Manual 4.200 g NaF in a 1 L volumetric flask and filling
Speed [%] . . . . . . . . . .
Time [s] . . . . . . . . . . .
. . . 50
. . . 30
up to 1 L with deionized water.
EQP titration The fluoride solution is kept in polyethylene bot-
Titrant/Sensor
Titrant . . . . . . . . . . . . . 1/2Pb(NO3)2 tles.
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.
∆V [mL] . . . . . . . . . . . . . 0.1
∆E [mV] . . . . . . . . . .
∆t [s] . . . . . . . . . .
.
.
.
.
.
.
0.5
3.0
Reaction
t(min) [s] . . . . . . . . . . . 5.0
t(max) [s] . . . . . . . . . . . 45.0
Recognition • Fluoride is precipitated by lead according to:
Threshold . . . . . . . . . . . . 300
Range . . . . . . . . . . . . . . No 2 F- + Pb2+ = PbF2
Termination
at maximum volume [mL] . . . . . 20.0 • This method can be used for the titration of sulphate
at slope . . . . . . . . .
.
.
.
.
.
.
No
No
ions.
n = . . . . . . . . . . . . . 1
Evaluation
Procedure . . . . . . . . .
Potential 1 . . . . . . . .
.
.
.
.
.
.
Standard
No
Chemicals
Potential 2 . . . . . . . . . . . No
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 . . . . . . . .
Formula t . . . . . . . . .
. . . 0.1
. . . x
Literature
Report
Output . . . . . . . . . . . . . . . Printer • DL40 application no. 102.
Results . . . . . . . . . . . . . . No
All results . . . . . . . . . . . . Yes • C.E. Efstathion, T.P. Hadjhoannon,
Raw results . . . . . . . . . . . . No
Table of measured values . . . . . . 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
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, Saul-
gau (Württemberg), Germany , 1972. (Geman)
4) Pascal Rast, "Automatisierte Titration zur effizienten Badüberwachung", Seminar SGO (Sch-
weizerische Gesellschaft für Oberflächentechnik), Zürich (CH), 28.10.1987,
Kees Mooibroek, "Analysenverfahren für die Galvanotechnik", DGO Lehrgand (Deutsche Ge-
sellschaft für Oberflächentechnik) , Schwäbisch Gmünd (D), 19.5.1987.
Kees Mooibroek, "Aktuelle Möglichkeiten der Prozessüberwachung bei aussenstromlos arbei-
tenden 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.
Notes
This applications brochure represents selected, possible application examples. These have been tested with all pos-
sible 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.
Mettler-Toledo AG
Analytical
CH-8603 Schwerzenbach, Schweiz
Telefon (01) 806 77 11, Fax (01) 806 73 50
Internet: http://www.mt.com
AT Mettler-Toledo GmbH., A-1100 Wien

Tel. +43-1-604 19 80, Fax +43-1-604 28 80
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) GmbH, 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
DK Mettler-Toledo A/S, DK-2600 Glostrup
Tel. +45-4327 0800, Fax +45-4327 0828
ES Mettler-Toledo S.A.E., E-08038 Barcelona
Tel. +34-3-223 22 22, Fax +34-3-223 02 71
FR Mettler-Toledo s.a., F-78222 Viroflay
Tel. +33-1-3097 1717, Fax +33-1-3097 1616
HK Mettler-Toledo (HK) Ltd., Kowloon
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
IT Mettler-Toledo S.p.A., I-20026 Novate Milanese
Tel. +39-2-333 321, Fax +39-2-356 29 73
JP Mettler-Toledo K.K., Osaka 540-6017
Tel. +81-6-949 59 01, Fax +81-6-949 59 45
KR Mettler-Toledo (Korea) Ltd., Seoul (135-090)
Tel. +82-2-518 20 04, Fax +82-2-518 08 13
KZ Mettler-Toledo CA, 480009 Almaty
Tel. +7- 3272-608 834, Fax +7-3272-608 835
MY Mettler-Toledo (M) Sdn. Bhd. 47301 Petaling Jaya
Tel. +60-3-703 27 73, Fax +60-3-703 17 72
MY Mettler-Toledo (S.E.A.), 47301 Petaling Jaya
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 © 04/2007 Mettler-Toledo AG, ME-xxxxxxxx
PO Box, VI-400, CH-8606 Greifensee, Schweiz Printed in Switzerland on 100% chlorine-free pa-
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METTLER TOLEDO Titrators

42 different methods covering various determinations in the electroplating analysis

We wish you a lot of success

Craig Gordon Cosimo A. De Caro

M065 Electroless nickel bath: Determination of sodium hypophosphite ............................. 12

M151 Determination of acetic, phosphoric and nitric acid in a mixture .............................. 20

M181 Back-titration of aluminum in acidic bath.................................................................. 40

M183 Determination of nickel and cadmium by complexometry ........................................ 44

M185 Iodometric titration of Cr(VI) in an electroplating bath ............................................. 48

M189 Determination of free cyanide in a copper bath ......................................................... 56

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

M192 Determination of lead(IV) in batteries ...................................................................... 76

M194 Determination of nickel in an electroplating bath ...................................................... 80

M195 Determination of silver in silver alloy........................................................................ 82

M197 Titration of Tin(II) in acidic tin bath .......................................................................... 86

M198 Photometric titration of zinc in a spin bath ................................................................ 88

M200 Titration of ﬂuoride in soldering salts ........................................................................ 92

M062 Electroless copper bath: Determination of copper

Sample: Electroless copper bath Instruments: METTLER TOLEDO DL70

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

Titrant: Sodium thiosulphate, Na2 S2O3

Standard: Potassium iodate, KIO3

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

No Identiﬁcation Volume Results

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

M063 Electroless copper bath: Determination of free complexing agents

Sample: Electroless copper bath Instruments: METTLER TOLEDO DL70

METTLER DL70 Titrator Mettler-Toledo AG

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

No Identiﬁcation Volume Results

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

Statistics without sample No. 1/3

Author: Kees Mooibroek

M064 Electroless copper bath: Sodium hydroxide and formaldehyde

No Identiﬁcation Volume Results

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

HCHO + Na2SO3 + H2O → CH2OH•SO3Na + NaOH

Author: Kees Mooibroek

M065 Electroless nickel bath: Determination of sodium hypophosphite

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

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

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

No Identiﬁcation Volume Results

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

Title Bath composition

065a Hypophosphite in Chem.Ni measured 18-Nov-1991 15:19

No Identiﬁcation Volume Results

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

Volume Increment Signal Change 1st deriv. Time

E1 0.0000 284.0 0:03

Method 065a / Content determination

Method 065b / Iodine concentration

Author: Kees Mooibroek

M066 Electroless nickel bath: Determination of nickel

Sample: Electroless nickel bath Instruments: METTLER TOLEDO DL70

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

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

No Identiﬁcation Volume Results

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

Literature E-V curve

M067 Electroless nickel bath: Determination of sodium orthophosphite

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

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