Electronics and electroplating applications - Mettler · PDF fileM193 Complexometric titration of lead in alloy ... Electronics and electroplating applications METTLER TOLEDO DL5x

METTLER TOLEDO Titrators

Electronics andelectroplating 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 electronics industry containing valuable information and practical hints. This is the 28th 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

Page 2/100 METTLER TOLEDO DL5x and DL7x Titrators Electronics and electroplating applications

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

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 3/100

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

METTLER TOLEDO


M062 Electroless copper bath: Determination of copper

Sample: Electroless copper bath 10 mL

Substance: Copper (II), M = 63.546, z = 1

Preparation: 40 mL sulphuric acid 25% 5 mL Potassium iodide 10 % 5 mL Potassium thiocyanate 10%

Titrant: Sodium thiosulphate, Na2 S2O3 c(Na2 S2O3) = 0.1 mol/L

Standard: Potassium iodate, KIO3 (see application M009)

Instruments: METTLER TOLEDO DL70 Matrix Printer Epson LX800 with serial interface 8148

Method: 062

Accessories: Titration beakers ME-101974

Indication: DM140-SC at Sensor 2

Results: METTLER DL70 Titrator * METTLER - TOLEDO * Application Laboratory

062 Chem. Copper Electrolyte measured 20-Jun-1991 13:2020-Jun-1991 11:28 Titrator ElectroplatingSW 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 CuSO

4

5.460 g/L CuSO4.5H

2O


4

5.529 g/L CuSO4.5H

2O


4

5.494 g/L CuSO4.5H

2O


4

5.482 g/L CuSO4.5H

2O


4

5.396 g/L CuSO4.5H

2O

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 RemarksBath composition

This bath is used for chemical copper deposition on printed circuit boards. It consists of sodium hydrox-ide, formaldehyde, weakly complexed copper, free complexing agent(s), and additives.

Sample preparationBe careful! If cyanide is present in the sample, the addition of a sulphuric acid solution must be performed in a ventilated fume hood (formation of HCN!).1) A weak copper complex is decomposed at room

temperature by the acid medium. A stronger com-plex is decomposed in the same way at elevated temperature.

2) After decomposition the sample is cooled at room temperature.

3) Then potassium iodide (KI) and potassium thio-cyanate (KSCN) are added.

4) Cu(II) is reduced with excess iodide (I-) and sub-sequently precipitated as CuI in the presence of thiocyanate (SCN-). KSCN is added to avoid ad-sorption of I2 on the surface of CuI :

2 Cu2+ + 4 I - → 2 CuI + I2

The amount of iodine formed is proportional to the Cu(II) content. Cover the beakers to avoid loss of iodine

5) The complete reduction of Cu(II) requires 5 min.

Titration of iodine

I2 is titrated at room temperature with Na2S2O3:2 S2O3

2- + I2 → S4O62- + 2 I-

• Stir moderately. Vigorous stirring causes loss of I2

• Alternative: Photometric indication with DP550 Phototrode; indicator: starch

• Titration time: approx. 4 minutesLiterature1. B. Bressel, Ausserstromloser Kupferelekrolyt,

DGO Deutsche Gesellschaft für Galvano- und Oberflächentechnik e.V., Horionplatz 6, Düssel-dorf (Germany), 1988

2. Copper bath's manufacturer

DisposalCopper solutions: special waste

Other titratorsDL50 Graphix, DL53/55/58, DL77 titrators.

Method 062 Chem. Copper Electrolyte Version 20-Jun-1991 11:28

Title Method ID . . . . . . . . . . . . . 062 Title . . . . . . . . . . . . . Chem. Copper Electrolyte Date/time . . . . . . . . . . . . . 20-Jun-1991 11:28Sample Number samples . . . . . . . . . . 5 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . Na

2S2O3

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DM140-SC Unit of meas . . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . INC ∆V [mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . 100.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 800.0 Limit B [mV, pH,...] . . . . . 0.0 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Copper (Cu) Formula . . . . . . . . . . . . . . R1=Q*C1/U Constant . . . . . . . . . . . . . . C1=63.546/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . CuSO

4

Formula . . . . . . . . . . . . . . R2=Q*C2/U Constant . . . . . . . . . . . . . . C2=159.60/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . CuSO

4.5H

2O

Formula . . . . . . . . . . . . . . R2=Q*C2/U Constant . . . . . . . . . . . . . . C2=249.68/z Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Author: Kees Mooibroek

METTLER TOLEDO


M063 Electroless copper bath: Determination of free complexing agents


Substance: Complexing agents

Preparation: 60 mL deionised water

Titrant: Copper sulphate, CuSO4 c(CuSO4) = 0.01 mol/L

Standard: EDTA (see application M007)


Method: 063


Indication: DP550 Phototrode at sensor 2 DIN-Lemo Adapter ME-89600 Indicator: 0.25 g Murexide, 1:500 tritura-tion with NaCl

Results: METTLER DL70 Titrator Mettler-Toledo AG Application Laboratory

063 Free Complexing Agents measured 23-Jul-1991 16:2423-Jul-1991 15:25 Titrator P5SW Version 2.0 User KM

RESULTS


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

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

Statistics without sample No. 1/3 Number results R1 n = 4 Mean value x = 20.411 mmol/L Free Compl. Standard deviation s = 0.0029 mmol/L Free Compl. Rel. standard deviation srel = 0.014 %


Method RemarksBath composition

• This bath is used for chemical copper deposition on printed circuit boards. It consists of sodium hy-droxide, formaldehyde, weakly complexed copper, free complexing agent(s), and additives.

• Depending on the use of the bath a single specific complexing agent or a mixture of various complex-ing agents is used. Results are given in mmol/L.

• The free complexing agents influence the rate of copper deposition and the stability of the bath.

Sample preparation1) The copper bath is diluted and then titrated with

0.01 M Cu(II) titrant. No pH buffer is added, the sample is alkaline.

2) It is recommended to use a trituration 1:500 mu-rexide: NaCl.

3) Add the indicator before starting analysis. Keep sample free of air bubbles during titration. Air bubbles and undissolved impurities affect with the photometric indication.

Titration

Free complexing agents are titrated with Cu(II)-solu-tion in alkaline solution: Cu 2+ + Agent → Cu-Agent 2+ At the equivalence point (simplified):Cu 2+ + Murexide - → Cu-Murexid + (violet-yellow) • Adjust the DP 550 at 1000 mV in deionised water

before starting titration (100% transmission).• Due to the steep signal change, an EQP titration

with fixed increments is used. The low threshold value allows for different amounts of indicator.

• A fixed predispensing shortens the titration time. • Titration time: approx. 4 minutes.

Literature1. B. Bressel, Ausserstromloser Kupferelekrolyt,

DGO Deutsche Gesellschaft für Galvano- und Oberflächentechnik e.V., Horionplatz 6, Düssel-dorf (Germany), 1988.

2. Copper bath's manufacturer


Other titratorsDL50 Graphix, DL53/55/58, DL77 titrators.

Method 063 Free Complexing Agents Version 23-Jul-1991 15:25

Title Method ID . . . . . . . . . . . . . 063 Title . . . . . . . . . . . . . Free Complexing Agents Date/time . . . . . . . . . . . . . 23-Jul-1991 15:25Sample Number samples . . . . . . . . . . 5 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . CuSO

4-(2)

Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . DP550 Unit of meas . . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.0 Titrant addition . . . . . . . . INC ∆V [mL] . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 2.0 ∆t [s] . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . 100.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 0.0 Limit B [mV, pH,...] . . . . . 1000.0 Maximum volume [mL] . . . . . . . 40.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Free compl. Formula . . . . . . . . . . . . . . R1=Q*C1/U Constant . . . . . . . . . . . . . . C1=1000 Result unit . . . . . . . . . . . . mmol/L Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes


E-V curve

METTLER TOLEDO


M064 Electroless copper bath: Sodium hydroxide and formaldehyde


Substance: Sodium hydroxide, formaldehyde

Preparation: Deionised water, 40 mL

Titrant 1: Hydrochloric acid, HCl, c(HCl) = 0.1 mol/LTitrant 2: Sodium sulfite, Na2SO3 c(Na2SO3) = 1 mol/L (pH = 10.5)

Standard: Tris(hydroxymethyl)aminomethane


Method: 064

Accessories: Titration beakers ME-101974 1 additional DV90 burette drive 1 additional DV1010 burette

Indication: DG111-SC at sensor 1

Results: 064 Hydroxide and Formaldehyde measured 18-Jun-1991 17:1818-Jun-1991 11:05 Titrator P5SW Version 2.0 User KM

RESULTS


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

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

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

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


MethodMethod 064 Hydroxide and Formaldehyde Version 18-Jun-1991 11:05

Title Method ID . . . . . . . . . . . . . 064 Title . . . . . . . . . . . . . . . Hydroxide and Formaldehyde Date/time . . . . . . . . . . . . . 18-Jun-1991 11:05Instruction Instruction . . . . . . . . . . . . Analysis to be done > . . . . . . . . . . . . . . . . . after correction of > . . . . . . . . . . . . . . . . . the copper content.Sample Number samples . . . . . . . . . . 5 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 5.0 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Measure Sensor . . . . . . . . . . . . . . DG111-SC-(2) Unit of meas . . . . . . . . . . . . As installed ∆E [mV] . . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . . 3.0 t(min) mode . . . . . . . . . . . . Fix t(min) [s] . . . . . . . . . . . 30.0 t(max) [s] . . . . . . . . . . . . 300.0Calculation Result name . . . . . . . . . . . . Dil. sample Formula . . . . . . . . . . . . . . R1=E Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . pH Decimal places . . . . . . . . . . . 1Titration Titrant . . . . . . . . . . . . . . HCl Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DG111-SC-(2) Unit of meas . . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Predispensing . . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . Continuous Control band [mV, pH,...]. . . 0.3 Delay [s] . . . . . . . . . . 10 End point mode . . . . . . . . . EPA Potential [mV, pH,...] . . . . 10.5 Tendency . . . . . . . . . . . . Negative Maximum volume [mL] . . . . . . . 30.0Calculation Result name . . . . . . . . . . . . NaOH Formula . . . . . . . . . . . . . . R2=Q1*C2/U Constant . . . . . . . . . . . . . . C2=40/1 Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . Correction Formula . . . . . . . . . . . . . . R3=14-(Q1*C3)/U Constant . . . . . . . . . . . . . . C3=40/1 Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesDispense Titrant . . . . . . . . . . . . . . Na

2SO

3 (pH 10.5)

Concentration [mol/L] . . . . . . . 1.0 Volume [mL]. . . . . . . . . . . . . 10.0 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . R2>0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 60 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . R2>0Titration Titrant . . . . . . . . . . . . . . HCl Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DG111-SC-(2) Unit of meas . . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EP Predispensing . . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.0 Titrant addition . . . . . . . . Continuous Control band [mV, pH,...]. . . 0.2 Delay [s] . . . . . . . . . . 10 End point mode . . . . . . . . . EPA Potential [mV, pH,...] . . . . 10.5 Tendency . . . . . . . . . . . . Negative Maximum volume [mL] . . . . . . . 30.0 Condition . . . . . . . . . . . . Yes

Calculation Result name . . . . . . . . . . . . Formaldehyde Formula . . . . . . . . . . . . . . R4=Q[2]*C4/U Constant . . . . . . . . . . . . . . C4=30.03/1 Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . R2>0Calculation Result name . . . . . . . . . . . . Correction Formula . . . . . . . . . . . . . . R5=8.5-(Q[2]*C5/U) Constant . . . . . . . . . . . . . . C5=30.03/1 Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R2>0Instruction Instruction . . . . . . . . . . . . Sodium hydroxide > . . . . . . . . . . . . . . . . . content too high. > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT*** Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R2>16Instruction Instruction . . . . . . . . . . . . Sodium hydroxide > . . . . . . . . . . . . . . . . . content too low. > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT*** Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R2<12Instruction Instruction . . . . . . . . . . . . Formaldehyde content > . . . . . . . . . . . . . . . . . too high > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT*** Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R4>10Instruction Instruction . . . . . . . . . . . . Formaldehyde content > . . . . . . . . . . . . . . . . . too low > . . . . . . . . . . . . . . . . . ***PLEASE CORRECT*** Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R4<7Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1Statistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R4 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Remarks• The electrode DG111-SC is calibrated in the

range of pH 9 to 12 (see application M004).

• Hydrochloric acid is standardized with THAM (see application M003).

• The pH value of the sodium sulphite solution (Titrant 2) has to be adjusted to the same end-pont value as in the titration (see 6). Otherwise complicated blank evaluations are necessary.

• Total analysis time: approx. 4 minutes.

• The titrator displays warnings if upper or lower result limits are exceeded.

1

2

3

4

5

6

7

8


Comments to method 0641. 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.



Literature1. B. Bressel, Ausserstromloser Kupferelekrolyt, DGO Deutsche Gesellschaft für Galvano- und Ober-

flächentechnik e.V., Horionplatz 6, Düsseldorf (Germany), 19882. Copper bath's manufacturer


Other titratorsDL77 titrator.

E-V curve: NaOH content E-V curve: Formaldehyde content

METTLER TOLEDO


M065 Electroless nickel bath: Determination of sodium hypophosphite

Sample: Electroless nickel bath 3 mL

Substance: Sodium hypophosphite monohydrate, NaH2PO2 • H2O, M = 105.99

Preparation: - H2SO4 (20%), 50 mL - I2 , c(1/2 I2) = 0.1 mol/L, 20 mL - Oxidation reaction time: 60 min (in the dark)

Titrant 1: Iodine, I2 , c(1/2 I2) = 0.1 mol/L,

Titrant 2: Na2S2O3 , c(Na2S2O3)= 0.1 mol/L

Standard: For Na2S2O3: Potassium iodate Instruments: METTLER TOLEDO DL70

Matrix Printer Epson LX800 with serial interface 8148

Method: 065a, 065b

Accessories: Titration beakers ME-23828 (brown glass beaker)

1 additional DV90 burette drive 1 additional DV1010 burette

Indication: DM140-SC at sensor 2Results:

065a Hypophosphite in Chem.Ni measured 18-Nov-1991 15:28 18-Nov-1991 14:51 Titrator P 5 SW Version 2.0 User KM

RESULTS


1/1 Chem.Ni 13/40 3.0 mL 29.06 g/L NaH2PO

2

35.01 g/L NaH2PO

2•H

2O

-9.01 g/L Correction 1/2 Chem.Ni 13/45 3.0 mL 28.93 g/L NaH

2PO

2

34.85 g/L NaH2PO

2•H

2O

-8.85 g/L Correction 1/3 Chem.Ni 13.50 3.0 mL 29.10 g/L NaH

2PO

2

35.06 g/L NaH2PO

2•H

2O


2PO

2

35.25 g/L NaH2PO

2•H

2O


2PO

2

34.94 g/L NaH2PO

2•H

2O

-8.94 g/L Correction

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

2PO

2


2PO

2•H

2O

Standard deviation s = 0.150 g/L NaH2PO

2•H

2O

Rel. standard deviation srel = 0.428 % Outlier test: no outliers!

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


Method 065a / Content determinationMethod 065a Hypophosphite in Chem.Ni Version 18-Nov-1991 14:51

Title Method ID . . . . . . . . . . . . . 065a Title . . . . . . . . . . . . . Hypophosphite in Chem.Ni Date/time . . . . . . . . . . . . . 18-Nov-1991 14:51Sample Number samples . . . . . . . . . . 5 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 3.0 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 89.978 Equivalent number z . . . . . . . . 2Stir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 5Titration Titrant . . . . . . . . . . . . . . Na

2S2O3

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DM140-SC Unit of meas . . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.0 Titrant addition . . . . . . . . DYN ∆E(set)[mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Relative ∆V(min) [%dosVol] . . . . . 0.5 ∆V(max) [%buVol]. . . . . . 2.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . 150.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 1000.0 Limit B [mV, pH,...] . . . . . -1000.0 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . NaH

2PO

2

Formula . . . . . . . . . . . . . . R1=(H3-Q1)*C1/U Constant . . . . . . . . . . . . . . C1=M/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . NaH

2PO

2•H

2O

Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U Constant . . . . . . . . . . . . . . C2=105.99/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . Correction Formula . . . . . . . . . . . . . . R3=26-((H3-Q1)*C3/U) Constant . . . . . . . . . . . . . . C3=105.99/1 Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Instruction Instruction . . . . . . . . . . . . Sodium hypophosphite > . . . . . . . . . . . . . . . . . monohydrate content > . . . . . . . . . . . . . . . . . too high.Pls.correct Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R2>29Instruction Instruction . . . . . . . . . . . . Sodium hypophosphite > . . . . . . . . . . . . . . . . . monohydrate content > . . . . . . . . . . . . . . . . . too low.Pls.correct Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . R2<23Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes Table of measured values . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1Statistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R4 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Remarks

Bath composition

• This bath consists of nickel salts, sodium hy-pophosphite, buffering compounds, stabilisers, accelerators, wetting and complexing agents. Decomposition products are formed during use of the bath.

Sample preparation (Method 065a)

1) 2 mL sample are diluted with 50 mL sulphuric acid solution 20%.

2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are dispensed with a burette ("Titrant 1") to the acidified sample using the auxiliary function "Dosing" of the titrator. After dispensing cover the titration beaker by e.g. a watch glass.

3) This oxidation is carried out at room tempera-ture in the dark. Cover the beaker to prevent loss of iodine:

I2 + H2PO2- + H2O = 2I- + HPO3

2- +3H+

The reaction requires 60 minutes to com-plete.

4) Oxidising agents stronger than iodine may cause side reactions with organic bath compo-nents or decomposition products.

5) The amount of substance of the dispensed io-dine solution is determined with method 065b (see next page).

Content determination (Method 065a)

1) The content of sodium hypophosphite is deter-mined by an iodometric backtitration. Excess iodine is dispensed (sample preparation) in order to oxidise hypophosphite in the acidic solution. The remaining excess iodine is ti-trated with sodium thiosulphate:

I2 + 2 S2O32- → 2I- + S4O6

2-

2) Sodium thiosulphate is standardized with po-tassium iodate (see application M009).

3) The titrator displays warnings if upper or lower result limits are exceeded.


Method 065a / Content determination

Results and table of measured values

065a Hypophosphite in Chem.Ni measured 18-Nov-1991 15:19 18-Nov-1991 14:51 Titrator P 5 SW Version 2.0 User KM

RESULTS


1/1 Chem.Ni 13.55 3.0 mL 29.26 g/L NaH2PO

2

35.25 g/L NaH2PO

2•H

2O

-9.25 g/L Correction

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

MEASURED VALUES Titrant Na

2S2O3 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 065b / Iodine concentration

Method 065b / Iodine solutionMethod 065b Aux. value for M065/M067 Version 19-Nov-1991 14:12

Title Method ID . . . . . . . . . . . . . 065b Title . . . . . . . . . . . . . Aux. value for M065/M067 Date/time . . . . . . . . . . . . . 19-Nov-1991 14:12Sample Number samples . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 0.0 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 5Dispense Titrant . . . . . . . . . . . . . . 1/2 I

2

Concentration [mol/L] . . . . . . . 0.1 Volume [mL] . . . . . . . . . . . . 20.0Stir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 20Titration Titrant . . . . . . . . . . . . . . Na

2S2O3

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DM140-SC Unit of meas . . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 15.0 Titrant addition . . . . . . . . DYN ∆E(set)[mV] . . . . . . . . . 4.0 Limits ∆V . . . . . . . . . . Relative ∆V(min) [%dosVol] . . . . . 0.1 ∆V(max) [%buVol]. . . . . . 1.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . 150.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 1000.0 Limit B [mV, pH,...] . . . . . -1000.0 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Consumption Formula . . . . . . . . . . . . . . R1=Q1 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 4Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Aux.M065/M067 Formula . . . . . . . . . . . . . . H3=�[1] Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . 1.5<�<2.5Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes


DisposalNickel solutions: special waste

Other titratorDL77 titrator.

Remarks

Sample preparation Method 065b1) 50 mL sulphuric acid solution 20% are given

into a titration beaker.

2) 20 mL iodine solution c(1/2 I2) = 0.1 mol/L are dispensed automatically by the titrator using the function "Dispense" in method 065b.

Titration

1) Iodine is titrated with sodium thiosulphate:

I2 + 2 S2O32- → 2 I- + S4O6

2-

2) Sodium thiosulphate is standardized with potas-sium iodate (see application M009).

3) The mean value of a series of three sample is automatically stored as auxiliary value H3 and can therefore by applied by method 065a for the determination of nickel.

4) The storage of the mean value only occurs if it is comprised between the limits 1.5 and 2.5 mmol which assure an adequate cocnentra-tion.

5) The shelf life of the iodine solution is limited. We recommend to perfom method 065b before

METTLER TOLEDO


M066 Electroless nickel bath: Determination of nickel

Sample: Electroless nickel bath 5 mL

Substance: Nickel, M = 58.69 g/mol

Preparation: - Deionised water, 50 mL - Buffer pH 10, 10 mL

- 0.25 g Murexide trituration with NaCl (1:500).

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

Standard: Zinc sulfate, c(ZnSO4) = 0.1 mol/L (See METTLER method M007)


Method: 066


Indication: - DP550 Phototrode at sensor 2 - Indicator: Murexide trituration

Results:

066 Ni in Chem. Ni-Electrolyte measured 13-Sep-1991 14:2313-Sep-1991 13:39 Titrator P5SW Version 2.0 User KM

RESULTS


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

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


Remarks• The buffer pH 10 is prepared by addition of

570 mL conc. NH3 and 70 g NH4Cl in a 1 L flask. Deionised water is added to 1 L.

• The shape of the titration curve is somewhat af-fected by the concentration of the indicator. The results, however, do not differ significantly (tested range: 25-500 mg 1:500 murexide : NaCl trituration pe sample).

• The results are given in g/L using the molar mass M.

M(Ni) = 58.69 g/mol

M(NiCl2) = 129.6 g/mol

M(NiCl2•6H2O) = 237.7 g/mol.

• Nickel ions forms a yellow complex with murexide in alkaline solution:

Ni 2+ + Murexide - = Ni-Murexide+

By adding EDTA, Ni forms a more stable complex with EDTA:

Ni-Murexide+ + EDTA 4- = Ni-EDTA2-+ Murexide-

At the equivalence point, all Ni ions have been complexed by EDTA and murexide is free in the alkaline solution. There is a colour change from yellow to blue-violet.

• Nickel content of different baths:

Bath n Content / g/L srel / %

LR-6/A 5 5.65 0.254 LR-37K 6 5.67 0.253 LR-200 6 5.74 0.211 ALT/IC 5 5.38 0.128 NM/a-1 6 5.36 0.206 IG/3-6 6 6.41 0.219

Method 066Method 066 Ni in Chem. Ni-Electrolyte Version 13-Sep-1991 13:39

Title Method ID . . . . . . . . . . . . . 066 Title . . . . . . . . . . . . . Ni in Chem. Ni-Electrolyte Date/time . . . . . . . . . . . . . 13-Sep-1991 13:39Instruktion Instruction . . . . . . . . . . . . 10mL NH

3-Buffer, pH 10

> . . . . . . . . . . . . . . . . . + ca. 200 mg 1 : 500 > . . . . . . . . . . . . . . . . . Murexide triturationSample Number samples . . . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 5.0 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 58.69 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DP550 Unit of meas . . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set)[mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) . . . . . . . . . . 0.05 ∆V(max) . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 2.0 ∆t [s] . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 15.0 Threshold . . . . . . . . . . . 10.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 1000.0 Limit B [mV, pH,...] . . . . . 0.0 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Ni Content Formula . . . . . . . . . . . . . . R1=Q*C1/U Constant . . . . . . . . . . . . . . C1=M/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Literature1. METTLER DL40RC Applications No. 107, 307. 2. METTLER DL25 Application No. 303. METTLER Applications No. M065 and M067


Other titratorsDL53/DL55 (without Function "Instruction"), DL58, DL77.


E-V curve

METTLER TOLEDO


M067 Electroless nickel bath: Determination of sodium orthophosphite

Sample: Electroless nickel bath 0.5 mL

Substance: Sodium orthophosphite, Na2HPO3 M = 125.96 g/mol, z = 2

Preparation: - 20 mL 5% NaHCO3 solution - 20 mL Iodine solution c(1/2 I2) = 0.1 mol/L

- Oxidation reaction time in the dark: 30 min.

Titrant 1: Iodine, c(1/2 I2) = 0.1 mol/LTitrant 2: Acetic acic, c(CH3COOH) = 2 mol/LTitrant 3: Sodium thiosulphate,

c(Na2S2O3) = 0.1 mol/L

Standard: For Na2S2O3 : Potassium iodate Instruments: METTLER TOLEDO DL70

Matrix Printer Epson LX800 with serial interface 8148

Method: 067

Accessories: Titration beakers ME-23828 (brown glasses) Two additional drives DV90 Two additional burettes DV1020

Indication: DM140-SC at Sensor 2

Results: 067 Orthophosphite in Chem. Ni measured 21-Nov-1991 17:2321-Nov-1991 12:44 Titrator P 5SW Version 2.0 User KM

RESULTS


1/1 Chem.Ni 28/10B 0.5 mL 190.03 g/L Na2HPO

3

156.87 g/L NaH2PO

3

123.71 g/L H3PO

3


3

156.57 g/L NaH2PO

3

123.47 g/L H3PO

3


3

156.69 g/L NaH2PO

3

123.57 g/L H3PO

3


3

156.88 g/L NaH2PO

3

123.71 g/L H3PO

3


3

156.83 g/L NaH2PO

3

123.67 g/L H3PO

3


3

156.73 g/L NaH2PO

3

123.60 g/L H3PO

3


3

156.41 g/L NaH2PO

3

123.35 g/L H3PO

3


3

156.80 g/L NaH2PO

3

123.65 g/L H3PO

3

STATISTICS Number results R1 n = 8 Mean value x = 189.86 g/L Na

2HPO

3

Standard deviation s = 0.196 g/L Na2HPO

3



2PO

3


2PO

3


RemarksElectroless nickel bath

• Orthophosphite affects the behaviour of the bath. The bath must be replaced as soon as a specific concentration is reached.

Sample preparation (Method 067)

1) Add 20 mL 5% NaHCO3 to the sample.

2) 20 mL iodine c(1/2 I2) = 0.1 mol/L are dispensed using the auxiliary function "Dosing" of the titra-tor. Cover the beaker to prevent loss of iodine.

3) This oxidation is carried out at room temperature in the dark during 30 minutes :

I2 + HPO32- + 3 OH - = 2I- + PO4

3- + 2 H2O

Procedure

• The orthophosphite concentration is determined by an iodometric back titration.

• The iodine concentration is determined by a similar method as 067. The result (mmol) is stored as aux-iliary value H3 and used for the back-titration.

• The sample is acidified with 20 mL 2 mol/L acetic acid immediately before titration.

• The iodine excess is then titrated with method 067.

• If the orthophosphite concentration exceeds the limit of 200 g/L an instruction is displayed.

Nickel content of different baths

Bath n Content/ g/L srel/%

28/10 A 3 189.00 0.158 28/10 B 8 189.66 0.103

Method 067



Other titratorsDL53/DL55 (without Function "Instruction"), DL58, DL77.

Method 067 Orthophosphite in Chem.Ni Version 21-Nov-1991 12:44

Title Method ID . . . . . . . . . . . . . 067 Title . . . . . . . . . . . . . Orthophosphite in Chem.Ni Date/time . . . . . . . . . . . . . 21-Nov-1991 12:44Sample Number samples . . . . . . . . . . 8 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 0.5 ID1 . . . . . . . . . . . . . . . . ******** Molar mass M . . . . . . . . . . . . 0.0 Equivalent number z . . . . . . . . 2Dispense Titrant . . . . . . . . . . . . . . Acetic acid Concentration [mol/L] . . . . . . . 2 Volume [mL] . . . . . . . . . . . . 20.0Stir Speed [%] . . . . . . . . . . . . . 40 Time [s] . . . . . . . . . . . . . . 20 Titration Titrant . . . . . . . . . . . . . . Na

2S2O3

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DM140-SC Unit of meas . . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.0 Titrant addition . . . . . . . . DYN ∆E(set)[mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Relative ∆V(min) [%dosVol] . . . . . 0.5 ∆V(max) [%buVol]. . . . . . 2.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . 150.0 EQP range . . . . . . . . . . . Yes Limit A [mV, pH,...] . . . . . 1000.0 Limit B [mV, pH,...] . . . . . -1000.0 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Na

2HPO

3

Formula . . . . . . . . . . . . . . R1=(H3-Q1)*C1/U Constant . . . . . . . . . . . . . . C1=125.9589/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . NaH

2PO

3

Formula . . . . . . . . . . . . . . R2=(H3-Q1)*C2/U Constant . . . . . . . . . . . . . . C2=103.9768/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . H

3PO

3

Formula . . . . . . . . . . . . . . R3=(H3-Q1)*C3/U Constant . . . . . . . . . . . . . . C3=81.9947/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Instruction Instruction . . . . . . . . . . . . CHECK CONCENTRATION > . . . . . . . . . . . . . . . . . OF PHOSPHITE > . . . . . . . . . . . . . . . . . Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . R2>200Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

E-V curve

METTLER TOLEDO


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

Sample: Acid mixture 1 mL

Substance: Acetic acid HAc Phosphoric acid H3PO4 Nitric acid, HNO3

Preparation: 50 mL deion. water

Titrant: Sodium hydroxide, NaOH c(NaOH) = 0.1 mol/L

Standard: Potassium hydrogen phtalate

Instruments: METTLER TOLEDO DL58 METTLER TOLEDO ST20A Printer EPSON SC600

Method: Mix

Accessories: Titration beakers ME-101974 Peristaltic pump ME-65241

Indication: DG111-SC

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

Method Mix HAc+HNO3+H3PO4 16-Mar-1999 17:18Measured 17-Mar-1999 16:20User Li Pei

ALL RESULTS

No. ID Sample size and results

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

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

STATISTICS Number results R2 n = 3 Mean value x = 0.9862 mol/L H3PO4 content Standard deviation s = 0.00300 mol/L H3PO4 content Rel. standard deviation srel = 0.304 % STATISTICS Number results R3 n = 3 Mean value x = 0.4429 mol/L HNO3 content Standard deviation s = 0.00384 mol/L HNO3 content Rel. standard deviation srel = 0.867 %


Remarks• This titration procedure includes four steps: 1. HNO3 = H+ + NO3

-

2. H3PO4 = H+ + H2PO4-

3. HAc = H+ + Ac-

4. H2PO4- = H+ + HPO4

2-

Due to the little difference between the pKa-value of HNO3 (pKa=approx. -1.3) and H3PO4 (pKa1=2.12), the first two steps can not be distinguished. Therefore only three potential jumps can be seen on the titration curve.

• A sample changer ST20A is used in this method for a fully automatic procedure. The method can be easily modified for manual operation: enter "Stand 1" as titration stand in the function SAMPLE.

Disposal

Neutralization with hydrochloric acid.

Other titratorsDL50 Graphix, DL53/DL55, DL70ES, DL77.

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

Title Method ID . . . . . . . . . . . . . Mix Title . . . . . . . . . . . . . HAc+HNO3+H3PO4 Date/time . . . . . . . . . . . . . 21-Nov-1991 12:44Sample Sample ID . . . . . . . . . . . . . Mix. Acid Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 100 Equivalent number z . . . . . . . . 2 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . 50.0 Stir . . . . . . . . . . . . . No Pump . . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . 10.0 Conditioning . . . . . . . . . . No Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 2.5 Wait time [s] . . . . . . . . . . 0 Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0 ∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . . 10.0 Recognition Threshold . . . . . . . . . . . . 17.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . None Termination at maximum volume [mL] . . . . . 40.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 3 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R1=Q2*C1/m Constant . . . . . . . . . . . . . . C1=1/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mol/L Result name . . . . . . . . . . . . HAc content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q3*C2/m Constant . . . . . . . . . . . . . . C2=1/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mol/L Result name . . . . . . . . . . . . H3PO4 content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=(Q1-Q3)*C3/m Constant . . . . . . . . . . . . . . C3=1/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mol/L Result name . . . . . . . . . . . . HNO3 content Statistics . . . . . . . . . . . . . YesReport 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

E-V curve

METTLER TOLEDO


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

Sample: Acid cleaner 0.5 g

Substance: Nitric acid, HNO3 ; Acetic acid HAc; Phosphoric acid H3PO4

HNO3 : HAc : H3PO4 = approx. 1 : 4 : 23

Preparation: 50 mL deion. water (dispensed by pump)

Titrant: Sodium hydroxide, NaOH c(NaOH) = 1 mol/L


Instruments: METTLER TOLEDO DL58 METTLER TOLEDO ST20A Printer EPSON SC600

Method: 2.2



Results: Method 2.2 EQP Titration 07/17/2000 13:59Measured 07/17/2000 14:48User 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 R1 = 3.0858 % HNO3 content R2 = 12.0854 % HAc content R3 = 70.8494 % H3PO4 content 3 0.518 g R1 = 2.9778 % HNO3 content R2 = 11.9648 % HAc content R3 = 70.9050 % H3PO4 content 4 0.5373 g R1 = 3.1480 % HNO3 content R2 = 11.8686 % HAc content R3 = 70.7380 % H3PO4 content 5 0.5176 g R1 = 3.0152 % HNO3 content R2 = 11.7205 % HAc content R3 = 70.7452 % H3PO4 content 6 0.5078 g R1 = 3.0452 % HNO3 content R2 = 11.6033 % HAc content R3 = 70.6551 % H3PO4 content STATISTICS Number results R1 n = 6 Mean value x = 3.0574 % HNO3 content Standard deviation s = 0.05917 % HNO3 content Rel. standard deviation srel = 1.935 %

STATISTICS Number results R2 n = 6 Mean value x = 11.9131 % HAc content Standard deviation s = 0.23308 % HAc content Rel. standard deviation srel = 1.957 % STATISTICS Number results R3 n = 6 Mean value x = 70.8119 % H3PO4 content Standard deviation s = 0.12031 % H3PO4 content Rel. standard deviation srel = 0.170 %



-

2. H3PO4 = H+ + H2PO4-

3. HAc = H+ + Ac-

4. H2PO4- = H+ + HPO4

2-

Due to the little difference between the pKa-value of HNO3 and H3PO4 ,the first two steps can not be distinguished. Therefore only three potential jumps can be seen on the titration curve.

• The two potential jumps are evaluated at potential values of pH 3.75 and 5.5 (see evaluation). These values are determined by a trial titration. From the table of measured values the pH values correspond-ing to the potential jumps can be easily determined. The values are then used for sample analysis.

Note that these values depend on the concentration of the sample and on sample preparation. Thus, it is necessary to first determine the potential values for any other mixture.

Disposal



Method

Author: Lin Yau Yeng (YY)

Method 2.2 EQP Titration Version 07/17/2000 13:59Title Method ID . . . . . . . . . . . . . 2.2 Title . . . . . . . . . . . . . EQP Titration Date/time . . . . . . . . . . . . . 07/17/2000 13:59Sample Sample ID . . . . . . . . . . . . . Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.4 Upper limit [g] . . . . . . . . . 0.6 Molar mass M . . . . . . . . . . . . 98 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . 50.0 Stir . . . . . . . . . . . . . No Pump . . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . 20.0 Conditioning . . . . . . . . . . Yes Time [s] . . . . . . . . . . . 20 Interval . . . . . . . . . . . 1 Rinse . . . . . . . . . . . . No Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . pH Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 3 Wait time [s] . . . . . . . . . . 10 Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 10.0 ∆V(min)[mL] . . . . . . . . . . 0.005 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.3 ∆t [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 52.0 Recognition Threshold . . . . . . . . . . . . 6.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . None Termination at maximum volume [mL] . . . . . 12.0 at potential . . . . . . . . . . Yes Potential [mV, pH,..] . . . . 10.5 at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . Yes Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . Yes Pot. 1 [mV, pH,..] . . . . . . 3.75 Potential 2 . . . . . . . . . . . Yes Pot. 2 [mV, pH,..] . . . . . . 5.5 Stop for reevaluation . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R=(QP1-(Q-QP2))*C/m Constant . . . . . . . . . . . . . . C=63.01/(10*z) Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . HNO3 content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=(QP2-QP1)*C2/m Constant . . . . . . . . . . . . . . C2=60.05/(10*z) Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . HAc content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=(Q-QP2)*C3/m Constant . . . . . . . . . . . . . . C3=M/(10*z) Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . H3PO4 content Statistics . . . . . . . . . . . . . YesReport 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

E-V curve

METTLER TOLEDO


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

Sample: Acid cleaner 10 mL

Substance: Nitric acid, HNO3, 0.1 % Acetic acid HAc, 0.1% Phosphoric acid H3PO4, 0.25%

HNO3 : HAc : H3PO4 = approx. 1 : 1 : 2




Instruments: METTLER TOLEDO DL70ES Printer EPSON SC600

Method: Y021



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

Method Y021 Mixed Acids-HNO3,H

3PO

4,HAc Apr/23/1999 10:34 am

User YYMeasured Apr/23/1999 1:36 pm

RESULTS

No ID1 ID2 Sample amount and results

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

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

STATISTICS Number results R2 n = 3 Mean value x = 0.1168 % Acetic Acid Standard deviation s = 0.001026 % Acetic Acid Rel. standard deviation srel = 0.878 % STATISTICS Number results R3 n = 3 Mean value x = 0.2509 % Phosphoric Standard deviation s = 0.000804 % Phosphoric Rel. standard deviation srel = 0.321 %



-

2. H3PO4 = H+ + H2PO4-

3. HAc = H+ + Ac-

4. H2PO4- = H+ + HPO4

2-

Due to the little difference between the pKa-value of HNO3 and H3PO4 , the first two steps can not be distinguished. Therefore only three potential jumps can be seen on the titration curve.

• The potential jumps are evaluated by means of control ranges. To set the optimum values for the control ranges, a trial titration must be first per-formed. From the table of measured values the ap-propriate control ranges can be selected and stored in the method.

Note that these values depends on the concentration of the sample and on sample preparation. Thus, it is necessary to first determine these values for any other acid mixture.

Disposal


Method

Author: Lin Yau Yeng (YY)

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

Title Method ID . . . . . . . . . . . . . Y021 Title . . . . . . . . . . . . . Mixed Acids-HNO

3,H

3PO

4,HAc

Date/time . . . . . . . . . . . . . Apr/23/1999 10:34 amSample Number samples . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 10.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 98 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.05 ∆V(min) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.2 ∆t [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 40.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 4 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Nitric Acid Formula . . . . . . . . . . . . . . R=(Q-Q(EPOT<-100))*C/U Constant . . . . . . . . . . . . . . C=63/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Acetic Acid Formula . . . . . . . . . . . . . . R2=Q(100>EPOT>-80)*C2 Constant . . . . . . . . . . . . . . C=60/(U*10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 4Calculation Result name . . . . . . . . . . . . Phosphoric Formula . . . . . . . . . . . . . . R3=Q(EPOT<-100)*C3/U Constant . . . . . . . . . . . . . . C=M*3/(10*3) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 4Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes ∆E/∆V - V curve . . . . . . . . . . Yes

E-V curve

Other titratorsDL50 Graphix, DL53/DL55, DL77.

METTLER TOLEDO


M154 Simultaneous titration of HCl, CH3COOH, and NH4Cl

Sample: 3 mL acid mixture (1 mL of each acid)

Substance: Hydrochloric acid HCl, 0.1 mol/L Acetic acid HAc, 0.1 mol/L Ammonium chloride, NH4Cl, 0.1 mol/L




Instruments: METTLER TOLEDO DL77 Printer EPSON SC600 METTLER TOLEDO ST20A

Method: WS2



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 0.3652 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 0.62 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 0.5352 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%


Remarks

• A mixture of three different acids (hydrochloric acid, acetic acid and ammonium chloride) with clear different acid dissociation constant (pKa = -10, 4.75, and 9.25, respectively) is titrated with 0.1 M NaOH.

• The mixture is prepared by adding 1 mL 0.1 mol/L of each acid soution into the titration beaker. The mixture is diluted with 40 mL deionized water before titration.

• Reactions: Dominating reaction in the pH-range 2.8-5.0: HCl + NaOH = Na+ + Cl- + H2O

Dominating reaction in the pH-range 5.0-9.0: CH3COOH + NaOH = CH3COO- + Na+ + H2O

Dominating reaction in the pH-range 9.0-11.5:

NH4Cl + NaOH = Na+ + Cl- + NH3 + H2O

Disposal:---

Method

Authors: H.-J. Muhr, E. Renaud Gueletti, J.Zarske

Other titratorsDL50 Graphix, DL53/DL55, DL70ES.

Method WS2 HCl/HOAc/NH4Cl Version Sep/10/1999 9:49 am

Title Method ID . . . . . . . . . . . . . WS2 Title . . . . . . . . . . . . . . . HCl/HOAc/NH4Cl Date/time . . . . . . . . . . . . . Sep/10/1999 9:49 amSample Number samples . . . . . . . . . . . 6 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Volume U Lower limit [mL] . . . . . . . . 0.5 Upper limit [mL] . . . . . . . . 2.5 ID1 . . . . . . . . . . . . . . . . Serie2 Molar mass M . . . . . . . . . . . . 36.46 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 20Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.03 dV(max) [mL] . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 2.2 Maximum volume [mL] . . . . . . . 4.0 Evaluation procedure . . . . . . Standard Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Result name . . . . . . . . . . . . HCl Formula . . . . . . . . . . . . . . R1=Q1*C1/U Constant . . . . . . . . . . . . . . C1=M/(10*z) Result unit . . . . . . . . . . . . mg/L Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . HOAc Formula . . . . . . . . . . . . . . R2=Q2*C2/U Constant . . . . . . . . . . . . . . C2=60.0/(10*z) Result unit . . . . . . . . . . . . mg/L Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . NH4Cl Formula . . . . . . . . . . . . . . R3=Q3*C3/U Constant . . . . . . . . . . . . . . C3=53.49/(10*z) Result unit . . . . . . . . . . . . mg/L Decimal places . . . . . . . . . . . 3Record Output unit . . . . . . . . . . . . Printer Results last sample . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes dE/dV - V curve . . . . . . . . . . YesRinse Auxiliary reagent . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 20.0Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

METTLER TOLEDO


M155 Polishing bath: determination of sulfuric and phosphoric acid

Sample: 1 mL polishing bath (density: 1.981 g/cm3)

Substance: Sulfuric acid Phosphoric acid

Preparation: - 1:10 dilution - 50 mL deion. water



Instruments: METTLER TOLEDO DL67 Printer EPSON LX400 METTLER TOLEDO ST20A

Method: hpo4



Results: METTLER DL67 Titrator V3.1

Method hpo4 H2SO

4+H

3PO

4 in Polstar 21-02-1994 10:15

User YYMeasured 21-02-1994 10:42

RESULTS


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

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


Remarks• Sample preparation: 1 mL polishing bath is first diluted with water

(1:10). Again, 1 mL of the diluted solution is added into the titration beaker together with 50 mL deion-ized water.

• Sulfuric and phosphoric acid can dissociate two protons H+ (sulfuric acid, H2SO4) and three protons H+ (phosphoric acid, H3PO4), respectively.

The dissociation constants pKa of H2SO4 are: pKa1 = approx. -3, pKa2 = 1.92. Sulfuric acid is a strong acid that dissociates com-

pletely in water. The dissociation constants pKa of H3PO4 are: pKa1 = 2.12 pKa2 = 7.21 pKa3 = 12.67 In aqueous solution only the first two dissociation

steps of phosphoric acid can be monitored, while the third one is too weak .

Based on the pK-values of the two acids in water, the following reactions can be given for the two EQPs found during titration:

1st EQP: H2SO4 + NaOH = Na+ + HSO4

- + H2O HSO4

- + NaOH = Na+ + SO42- + H2O

H3PO4 + NaOH = H2PO4- + Na+ + H2O

2nd EQP: H2PO4

- + NaOH = HPO42- + Na+ + H2O

DisposalNeutralization with hydrochloric acid.

Method

Authors: Application Laboratory MT-Germany


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

Title Method ID . . . . . . . . . . . . . WS2 Title . . . . . . . . . . . . . . . H

2SO

4+H

3PO

4 in Polstar

Date/time . . . . . . . . . . . . . 21-02-1994 10:15Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.0 Upper limit [mL] . . . . . . . . 2.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 98 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.5 Sensor . . . . . . . . . . . . . . . DG111-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . mL Volumen [mL] . . . . . . . . 0.1 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.05 dV(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes

n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Phosphoric Formula . . . . . . . . . . . . . . R1=Q2*C1/m Constant . . . . . . . . . . . . . . C1=98/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 2Calculation Result name . . . . . . . . . . . . Sulfuric Formula . . . . . . . . . . . . . . R2=((Q1*2)-(Q1+Q2))*C2 Constant . . . . . . . . . . . . . . C2=98/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 2Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Output unit . . . . . . . . . . . . Printer Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesRinse Auxiliary reagent . . . . . . . . . H2O Volume [mL] . . . . . . . . . . . . 20.0

E-V curve

METTLER TOLEDO


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

Sample: Boric acid solution, 5 mL

Substance: Hydrochloric acid, HCl Hydrofluoric acid, HF

Boric acid, H3BO3

Preparation: - 30 mL deion. water - 20 mL Mannitol solution (c(Mannitol) = approx. 200g/L)



Instruments: METTLER TOLEDO DL70 Printer EPSON FX850 with serial interface

Method: A001

Accessories: Titration beakers ME-101974 Additional burette drive DV90

Additional burette DV1020


Results: METTLER DL70 Titrator

A001 Borsäure measured 14-Nov-1989 12:44 14-Nov-1989 12:28 TitratorSW 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


Remarks• Sample preparation: 200g mannitol are dissolved in 1 L volumetric flask

with deion. water. Boric acid can not be titrated directly in electro-

plating solution since it is a weak acid. To allow titration, mannitol is added to the sample. Mannitol forms a complex with boric acid giving in a medium strong acidic compounds.

• A sample changer ST20A can be used in this method for a fully automatic procedure. The method can be easily modified for automatic operation: enter "ST20 1" as titration stand in the function SAM-PLE.

• CAUTION: Hydrofluoric acid is poisonous! Work in a fume hood, wear safety goggles and gloves.

DisposalNeutralization with hydrochloric acid.

Method

Author: Dieter Rehwald


Method A001 Borsäure Version 14-Nov-1989 12:28

Title Method ID . . . . . . . . . . . . . A001 Title . . . . . . . . . . . . . . . Borsäure Date/time . . . . . . . . . . . . . 14-Nov-1989 12:28Sample Number samples . . . . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [mL] . . . . . . . . 0.05 Upper limit [mL] . . . . . . . . 0.15 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 61.83 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG115-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EP Predispensing . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . 8.0 ∆V(min) [mL] . . . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . . . 0.1 ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 0.5 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 20.0 Endpoint mode . . . . . . . . . . EPA Potential [mV,pH,...]. . . . . 0.0 Tendency . . . . . . . . . . . . Negative Maximum volume [mL] . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . mL HCl/HF Formula . . . . . . . . . . . . . . R=VEQ[1] Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . 3Record All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesDispense Titrant . . . . . . . . . . . . . . Mannitol Concentration [mol/L] . . . . . . . 0.0 Volume [mL] . . . . . . . . . . . . 20.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 60 Titration Titrant . . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DG115-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volumen [mL] . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL]. . . . . . . . 0.02 ∆V(max) [mL]. . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 20.0 Maximum volume [mL] . . . . . . . 10.0 Evaluation procedure . . . . . . Standard Calculation Result name . . . . . . . . . . . . mL Brsaeure Formula . . . . . . . . . . . . . . R2=VEQ[2] Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . 3Record All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes

E-V curve:

Titration of HCl/HF

Titration of boric acid


Note:

Determination of nitric and hydrofluoric acid in stainless steel polishing bath

Sample: 1st titration: 0.5 g polishing bath 2nd titration: 1 g polishing bath

Substance: Nitric acid, HNO3 Hydrofluoric acid, HF

Preparation: 1st titration function:1.1 Weigh 0.5 g of acid sample.1.2 Take 10 mL potassium fluo-

ride solution (KF, e.g. 10%) and dilute it to 50 mL with deionized water.

1.3 Add the diluted KF solution to the sample.

2nd titration function:2.1 Weigh 0.5 g of acid sample.2.2 Add 50 mL acetone2.3 Add 4 g of sodium sulphate

Titrant: Potassium hydroxide, KOH c(NaOH) = 1.0 mol/L


Instruments: METTLER TOLEDO DL70ES Printer EPSON FX850 with serial interface

Method: HF1 (This method consists of two titration functions).


Indication: InLab429

Remarks

• Principle of the method: This method allows the determination of the nitric and hydrofluoric acid content in stainless steel

polishing bath. It consists of two sample and two titration functions. For a complete analysis, two samples are needed. With the first sample, the total acid strength of

the bath is determined by titration with KOH (first titration function), while the second sample is used for the determination of the HNO3-content (second titration). The difference of these results determines the HF-content.

• Total acid strength: Steel mainly contains iron, chromium and nickel and other metal ions. These metal ions can affect

the analysis, e.g. they can form hydroxide complexes due to the titrant addition of KOH. Therefore, an excess of potassium fluoride solution is added to avoid interference. In fact, fluoride

ions form complexes with metal ions (e.g. Al), and thus, it can mask them.

• HNO3-content: Hydrofluoric acid (HF) and nitric acid (HNO3) are both strong acids in aqueous solution (dissociation

constant pKa(HNO3) = -1.32 at 12.5°C; and pKa(HF) = 3.45), they dissociate completely. Since the pKa values are close to each other, the two potential jumps can not be distinguished during titration with a strong base in an aqueous solution: there is only one potential jump in the titration curve.

To discriminate the two potential jumps, the solvent is replaced by acetone, where the difference in pKa values of the two acids is large enough to separate them. The first EQP of the second titration function corresponds to nitric acid. Further addition of sodium sulphate, a well-known drying agent due to its hygroscopic property, allows the achievement of a complete anhydrous environment.


Remarks

• A sample changer ST20A can be used in this method for a fully automatic procedure. The method can be easily modified for automatic operation: enter "ST20 1" as titration stand in the function SAMPLE.

• CAUTION: HF is a very strong acid and it etches glass. Wear gloves and safety goggles.

Disposal


Method

Author: Craig Gordon


Titration Titrant . . . . . . . . . . . . . . KOH Concentration [mol/L] . . . . . . . 1.0 Sensor . . . . . . . . . . . . . . . InLab 429 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 100.0 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Termination at slope . . . . . . Yes Slope [mV,pH,.../mL] . . . . . 50.0 Combined termn criteria . . . . . Yes Evaluation procedure . . . . . . Standard Steepest jump only . . . . . . . Yes Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Result name . . . . . . . . . . . . HNO

3 Content

Formula . . . . . . . . . . . . . . R2=Q[2]*C2/m Constant . . . . . . . . . . . . . . C2=1/z Result unit . . . . . . . . . . . . mmol/g Decimal places . . . . . . . . . . . 4 Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesCalculation Result name . . . . . . . . . . . . HNO

3 Content

Formula . . . . . . . . . . . . . . R3=R2*C3/m Constant . . . . . . . . . . . . . . C3=63.0129/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . HF

Content

Formula . . . . . . . . . . . . . . R4=(R1-R2)*C4 Constant . . . . . . . . . . . . . . C4=20.0063/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 3 Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

Method HF1 HF and HNO3 Content Version Dec/03/1998 11:25 am

Title Method ID . . . . . . . . . . . . . HF1 Title . . . . . . . . . . . . . . . HF and HNO

3 Content

Date/time . . . . . . . . . . . . . Dec/03/1998 11:25 amSample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [mL] . . . . . . . . 0.0 Upper limit [mL] . . . . . . . . 1.0 ID1 . . . . . . . . . . . . . . . . HNO

3

Molar mass M . . . . . . . . . . . . 63.0129 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30Titration Titrant . . . . . . . . . . . . . . KOH Concentration [mol/L] . . . . . . . 1.0 Sensor . . . . . . . . . . . . . . . InLab 429 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 1.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 100.0 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Termination at slope . . . . . . Yes Slope [mV,pH,.../mL] . . . . . 50.0 Combined termn criteria . . . . . Yes Evaluation procedure . . . . . . Standard Steepest jump only . . . . . . . Yes Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0 Calculation Result name . . . . . . . . . . . . Total acid Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=1/z Result unit . . . . . . . . . . . . mmol/g Decimal places . . . . . . . . . . . 4Record Output unit . . . . . . . . . . . . Printer Result last sample . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesSample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [mL] . . . . . . . . 0.0 Upper limit [mL] . . . . . . . . 1.0 ID1 . . . . . . . . . . . . . . . . HF Molar mass M . . . . . . . . . . . . 20.0063 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualInstruction Attach sample with sodium sulphate added and acetone as a solventStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 60

METTLER TOLEDO


M157 Determination of hydrochloric and nitric acid

Sample: Acid mixture, 1 g

Substance: Nitric acid, HNO3 , appr. 25% Hydrochloric acid, HCl , appr. 3%

Preparation: method jud3: 50 mL deion. water method jud2: 1 mL 10% HNO3 in the sample titrated with method jud3

Titrant 1: Sodium hydroxide, NaOH c(NaOH) = 1 mol/L

Titrant 2: Silver nitrate, AgNO3 c(AgNO3) = 1 mol/L

Standard: NaOH: Potassium hydrogen phthalate AgNO3: Sodium chloride

Instruments: METTLER TOLEDO DL58 Printer EPSON SC600

Methods: jud3: Determination of total acid con-tent. jud2: Determination of hydrochloric and nitric acid content.

Accessories: Second burette drive DV90 Sec-ond burette DV1010

pH Option Titration beakers ME-101974

Peristaltic pump ME-65241

Indication: DG111-SC DM141-SC

Results:

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

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

ALL RESULTS


1 HCl/HNO3 1.011 g

R1 = 29.291 % HCl content R2 = 2.676 % HNO

3

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


ALL RESULTS


1 HCl/HNO3 1.011 g

R1 = 29.291 % mmol H+


Remarks1. Method jud3: det. of total acid content.2. Add 1 mL 10% HNO3 for chloride precipitation3. Method jud2: determination of HCl by precipita-

tion of chloride with AgNO34. Difference 1.-2. = content HNO3Please note that both methods can be summarized in a single method.

Method jud3

Author: Judy Maag

DisposalFiltration/Neutralization with sodium hydroxide.Other titratorsDL50 Graphix, DL53/DL55, DL70ES, DL77.

Method jud2Method jud3 Total acid cont (HCl+HNO3) Version 08/08/2000 12:20

Title Method ID . . . . . . . . . . . . . jud3 Title . . . . . . . . . . . . . Total acid cont (HCl+HNO

3)

Date/time . . . . . . . . . . . . . 08/08/2000 12:20Sample Sample ID . . . . . . . . . . . . . HCl/HNO

3

Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 100 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . pH Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 4.0 ∆V(min)[mL] . . . . . . . . . . 0.01 ∆V(max)[mL] . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 50.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . None Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . H+

Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoAuxiliary value ID . . . . . . . . . . . . . . . . . Total acid Constant . . . . . . . . . . . . . . H5=RReport Output . . . . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes 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

Method jud2 HCl det. with AgNO3 Version 08/08/2000 12:49

Title Method ID . . . . . . . . . . . . . jud2 Title . . . . . . . . . . . . . HCl det. with AgNO

3 Date/time . . . . . . . . . . . . . 08/08/2000 12:49Sample Sample ID . . . . . . . . . . . . . HCl/HNO

3

Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 36.45 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . AgNO

3 Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DM141 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0 ∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 1000.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . None Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . HCl content Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . R2=(H5-Q)*C2/m Constant . . . . . . . . . . . . . . C2=63.01/(10*z) Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . HNO

3 Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output . . . . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes 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

METTLER TOLEDO


M158 Determination of ammonia and hydrogen peroxide

Sample: Alkaline mixture, 0.5-1 g

Substance: Ammonia, NH3 Hydrogen peroxide, H2O2

Preparation: method amm1: 50 mL deion. water method hydr1: 1 mL 10% HNO3 in the sample titrated with method amm1


Titrant 2: Nitric acid, HNO3 c(HNO3) = 2 mol/L

Titrant 3: Potassium permanganate, KMnO4 c(1/5 KMnO4) = 0.1 mol/L

Standard: NaOH: Potassium hydrogen phthalate HNO3: THAM (Tris)

KMnO4: sodium oxalate, Na2C2O4


Methods: amm1: Back titration of NH3

hydr1: Redox titration of H2O2




Results:

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


ALL RESULTS


1 NH3/H

2O2 0.662 g

R1 = 0.936 % H2O2 content

Method amm1 Back titration of NH3 08/11/2000 13:29


ALL RESULTS


1 NH3/H

2O2 0.662 g

R1 = 3.484 % NH3 Content


Method amm1

Author: Judy Maag

DisposalThe sample has to be classified as special waste.


Method hydr1Method amm1 Back titration of NH3 Version 08/11/2000 13:29

Title Method ID . . . . . . . . . . . . . amm1 Title . . . . . . . . . . . . . Back titration of NH

3 Date/time . . . . . . . . . . . . . 08/11/2000 13:29Sample Sample ID . . . . . . . . . . . . . NH

3/H

2O2

Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 17 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . HNO

3 Concentration [mol/L] . . . . . . . 2.0 Volume [mL] . . . . . . . . . . . . 4.5Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . pH Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0 ∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 100.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . NH

3 Content

Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

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

Title Method ID . . . . . . . . . . . . . hydr1 Title . . . . . . . . . . . . . H

2O2 determination

Date/time . . . . . . . . . . . . . 08/11/2000 12:50Sample Sample ID . . . . . . . . . . . . . NH

3/H

2O2

Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 34.02 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/5 KMnO

4 Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0 ∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 15.0 Recognition Threshold . . . . . . . . . . . . 2000.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 8.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . H

2O2 content

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output . . . . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes 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

Remarks1. Method amm1: det. of NH3 by back titration.2. Add 1 mL 10% HNO3 for peroxide determina-

tion3. Method hydr1: determination of HCl by redox

titration with 1/5 KMnO4.Please note that both methods can be resumed in a

METTLER TOLEDO


M159 Determination of hydrochloric acid and hydrogen peroxide

Sample: Acid mixture, 0.5-1 g

Substance: Hydrochloric acid, HCl Hxdrogen peroxide, H2O2

Preparation: method hcl1: 50 mL deion. water method hydr1: 1 mL 10% HNO3 in the sample titrated with method hcl1


Titrant 2: Potassium permanganate, KMnO4 c(1/5 KMnO4) = 0.1 mol/L

Standard: NaOH: Potassium hydrogen phthalate KMnO4: sodium oxalate, Na2C2O4


Methods: hcl1: Titration of HCl

hydr1: Redox titration of H2O2




Results:

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


ALL RESULTS


1 HCl/H2O2 0.777 g

R1 = 2.075 % H2O2 content

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


ALL RESULTS


1 HCl/H2O2 0.777 g

R1 = 1.188 % HCl Content


Method hcl1

Author: Judy Maag

DisposalThe sample to be classified as special waste.


Method hydr1Method hydr1 H2O2 determination Version 08/11/2000 14:03

Title Method ID . . . . . . . . . . . . . hydr1 Title . . . . . . . . . . . . . H

2O2 determination

Date/time . . . . . . . . . . . . . 08/11/2000 14:03Sample Sample ID . . . . . . . . . . . . . HCl/H

2O2

Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 34.02 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/5 KMnO

4 Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0 ∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 15.0 Recognition Threshold . . . . . . . . . . . . 2000.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 8.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . H

2O2 content

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output . . . . . . . . . . . . . . . Printer Results . . . . . . . . . . . . . . No All results . . . . . . . . . . . . Yes Raw results . . . . . . . . . . . . Yes 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

Remarks1. Method hcl1: det. of HCl by direct titration.2. Add 1 mL 10% HNO3 for peroxide determina-

tion3. Method hydr1: determination of H2O2 by redox

titration with 1/5 KMnO4.

Method hcl1 Titration of HCl Version 08/11/2000 14:01

Title Method ID . . . . . . . . . . . . . hcl1 Title . . . . . . . . . . . . . Titration of HCl Date/time . . . . . . . . . . . . . 08/11/2000 14:01Sample Sample ID . . . . . . . . . . . . . HCl/H

2O2

Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 36.35 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . pH Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set)[mV] . . . . . . . . . . 8.0 ∆V(min)[mL] . . . . . . . . . . 0.02 ∆V(max)[mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 100.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . HCl Content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M181 Back-titration of aluminum in acidic bath

Sample: Acid mixture, 1 mL

Substance: Aluminium, Al, 15 g/L Sulfuric acid, H2SO4 Oxalic acid, H2C2O4

Preparation: 1. 20 mL deion. water 2. 20 mL buffer solution pH 4

3. Dispense exactly 20 mL 0.1 mol/L EDTA 4. Warm up during 10 min.

until boiling point.

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

Standard: ZnSO4: EDTA Standard EDTA: ZnSO4 Standard

Instruments: METTLER TOLEDO DL58 Printer

Methods: 40001

Accessories: Glass beakers ME-101446 Additional DV1020 burette

Indication: - Hg-DM141 (Amalgamated DM141)

- 3 drops 0.05 mol/L HgEDTA

Results: Sample Al content Comments Acidic bath (g/L)

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

Sample Al Purity Comments KAl(SO

4)2•12 H

2O (%)

n = 5 INC = 0.1 mL Threshold= 100mV/mLx 99.542 ∆E = 0.5 mV srel 0.05% ∆t = 3.0

DL40 Appl. no. 110


Method


DisposalThe sample to be classified as special waste (Hg).


RemarksAluminium acidic bath (Elox bath)

• This acidic bath contains aluminium, sulfuric and oxalic acid.

• The method was developed on the DL40 titrator (see DL40 applications No. 3, 110, 315) and has been adapted for the DL5x- and DL7x-titrators.

Sample preparation1) Add 20 mL deionized water to the sample.

2) Add 20 mL buffer solution pH 4 to avoid formation of aluminium hydroxide.

3) 20 mL 0.1 mol/L EDTA are dispensed using the auxiliary function "Dosing" of the titrator.

4) The sample beaker is heated to boiling during 10 minutes since the complexation of aluminium with EDTA is very slow at room temperature. Cover the glass titration beaker during heating.

5) Add three drops 0.05 mol/L Hg-EDTA

Procedure

• The aluminum concentration is determined by a back titration of excess EDTA with zinc sulfate.

• A blank titration is performed before analysis. The result (mmol) is stored as auxiliary value H1 and used for the back-titration.

• The EDTA excess is titrated with method 40001.

Method 40001 Aluminium Version 11/01/2001 16:30

Title Method ID . . . . . . . . . . . . . 40001 Title . . . . . . . . . . . . . Aluminium Date/time . . . . . . . . . . . . . 11/01/2001 16:30Sample Sample ID . . . . . . . . . . . . . Al/H

2SO

4/C

2O42-

Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 26.982 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . ZnSO

4 Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . HgDM141 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . Yes Volume [mL] . . . . . . . . . . . 5.0 Titrant addition . . . . . . . . . . INC ∆V [mL] . . . . . . . . . . . . . 0.3 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 25.0 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=(H1-Q)*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Al Content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

Chemicals

• Buffer solution pH 4: Dissolve 120 mL glacial acetic acid (i.e. 100%) and 54 g sodium acetate trihydrate in a 1 L flask. Add 10 mL 0.05 mol/L HgEDTA, and dilute to 1 L with deionized water.

• 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA and 0.05 mol/L Hg-acetate are mixed together. This solution is used as an indicator for the titration and is dissolved into the buffer solution instead of adding three drops for each sample.

Amalgamation of DM141 electrode (Hg-DM141)

• Clean the DM141 electrode with 2 mol/L HNO3, possibly polished , well rinsed and dried. The DM141 is dipped for 1 minute into mercury. The excess mercury is wiped off. Several titrations can be indicated before re-amalgamation.

• Note: the Hg-DM141 is inactivated by hydrogen peroxide, H2O2, and by S2-, CN- , .... .

METTLER TOLEDO


M182 Titration of sulphuric acid and aluminum in an electroplating bath

Sample: Acidic bath, 2 mL

Substance: Free sulfuric acid, H2SO4 (M = 98 ; z = 2)

Aluminium, Al(III) (M = 26.98 ; z = 3)

Preparation: 50 mL deionized water

Titrant: Sodium hydroxide, NaOH: c(NaOH) = 1 mol/L

Standard: Potassium hydrogen phtalate (see application M531)

Instruments: METTLER TOLEDO DL53 Epson matrix printer LX800

with serial inteface 8148

Method: 25002



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 H

2SO

4

+ 2 mL Al2(SO

4)3 2.3 g/L Al

Theoretical 49 g/Lcontent (g/L)

Content Aluminum: 2.347 g/L 5 1.233%

Theoretical content (g) 2.3 g/L Al


Author: Roland Böhlen, MT-Switzerland

DisposalNeutralization with HCl, special waste


Remarks• The method was developed on the DL25 titrator

and has been adapted for the DL5x-/7x-titrators.

Procedure• The determination of free acid and aluminum in an

acidic aluminun bath is determined with a single titration using sodium hydroxide.

• The titration curve gives three equivalence points:

1st EQP: Neutralization of free acid H2SO4 + 2 NaOH = Na2SO4 + 2 H2O

2nd EQP: Precipitation of aluminum hydroxide Al2(SO4)3 + 6 NaOH = 2 Al(OH)3 + 3 Na2SO4

3rd EQP: Dissolution of Al(OH)3 Al(OH)3 + NaOH = Al(OH)4

- + Na+

Literature

• Application no. M531, in Application brochure 18,

MethodMethod 25002 Free acid + Al Version 26/01/2001 15:46

Title Method ID . . . . . . . . . . . . . 25002 Title . . . . . . . . . . . . . Free acid + Al Date/time . . . . . . . . . . . . . 26/01/2001 15:46Sample Sample ID . . . . . . . . . . . . . H

2SO

4/Al

Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 2.0 Molar mass M . . . . . . . . . . . . 26.98 Equivalent number z . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . NaOH Concentration [mol/L] . . . . . . 1.0 Sensor . . . . . . . . . . . . . DG111 Unit of meas. . . . . . . . . . . As installed Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 4.0 ∆V(min) [mL] . . . . . . . . . . 0.02 ∆V(min) . . . . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 4 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 4.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R1=Q1*C1/m Constant . . . . . . . . . . . . . . C1=98.07/2 Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . H

2SO

4 Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q2*C2/m Constant . . . . . . . . . . . . . . C2=M/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Aluminum Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

Titration curves: standard solution

METTLER TOLEDO


M183 Determination of nickel and cadmium by complexometry

Sample: Standard solutions, 5 mL

Substance: Cadmium, Cd Nickel, Ni

Preparation: A) Only Cd, masking of Ni: - 10 mL buffer pH 10 solution

- 0.5 g dimethyl glyoxime, sodium salt octahydrate (C4H6N2Na2O2 • 8 H2O) - 40 mL deionized water B) Ni, Cd, Ni + Cd: - 10 mL buffer pH 10 solution - 40 mL deionized water Titrant: EDTA, e.g. c(EDTA) = 0.1 mol/L

Standard: ZnSO4

Instruments: METTLER TOLEDO DL58 Printer

Methods: 40002

Accessories: Titration beakers ME-101974 DV1010 burette

Indication: - Hg-DM141 (Amalgamated DM141)

- 3 drops 0.05 mol/L HgEDTA for each sample.

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 curve1 : 1 0.1 2.921 (Ni) 5 --

Ni + Cd 0.1 0.1 11.618 (Cd) 2 -- Steep titration curve1 : 1 0.1 0.1 5.8060 (Ni) 4 --

Ni + Cd 0.1 0.05 11.33 (Cd) 5 0.121 : 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


DisposalThe sample to be classified as special waste (Hg).


Remarks• The method was developed on the DL40 titrator (see

DL40 applications No. 317) and has been adapted for the DL5x- and DL7x-titrators.

Sample preparationA) Cadmium determination:

1) Add 10 mL buffer solution pH 10. 2) Add 0.5 g dimethylglyoxime disodium salt to

mask nickel ions.3) Add 40 mL deionized water.4) Add 3 drops 0.05 mol/L HgEDTA.

B) Ni determination:1) Add 10 mL buffer solution pH 10. 2) Add 40 mL deionized water.3) Add 3 drops 0.05 mol/L HgEDTA.

Procedure

• Cd content:1) Ni is masked with dimethylglyoxime diso-

dium salt. The sample is titrated with method 40002.

2) The Cd content is stored as auxil. value H6.

• Ni content:1) EDTA forms complexes with both Ni and Cd. 2) To distinguish both metal ions, the Cd content is

accounted for as a blank value in the calculation: R = (Q - H6)*C/m .

3) Since nickel is determined, C = M(Ni)/z, and therefore M = 58.59 .

Chemicals

• Buffer solution pH 10: 70 mL of concentrated am-monia solution (d=0.9 g/mL) and 70 g ammonium chloride (or 110 g NH4NO3) are dissolved in a 1 L flask with deionized water.

• 0.05 mol/L HgEDTA: Equal volumes of 0.05 EDTA and 0.05 mol/L Hg-acetate are mixed together.

Amalgamation of DM141 electrode (HgDM141)

• Clean the DM141 electrode with 2 mol/L HNO3, possibly polished , well rinsed and dried. The DM141 is dipped for 1 minute into mercury. The excess mercury is wiped off. Several titrations can be indicated before re-amalgamation.

• Note: the Hg-DM141 is inactivated by hydrogen peroxide, H2O2, and by S2-, CN- , .... .

Method 40002 Ni + Cd Version 12/01/2001 15:50

Title Method ID . . . . . . . . . . . . . 40002 Title . . . . . . . . . . . . . Ni + Cd Date/time . . . . . . . . . . . . . 12/01/2001 15:50Sample Sample ID . . . . . . . . . . . . . Ni/Cd Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 112.41 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . HgDM141 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . Yes Volume [mL] . . . . . . . . . . . 1.0 Titrant addition . . . . . . . . . . INC ∆V [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.2 ∆t [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 150 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Cd Content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Cd Content Statistics . . . . . . . . . . . . . YesAuxiliary value ID . . . . . . . . . . . . . . . . . mmol Cd Constant . . . . . . . . . . . . . . H6=R2Report 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

METTLER TOLEDO


M184 Determination of cadmium in alkaline baths

Sample: 1 mL alkaline bath

Substance: Cadmium, Cd

Preparation: - 50 mL deion. water. - 0.25 g 1:500 Murexide:NaCl

trituration

Titrant: EDTA c(EDTA) = 0.1 mol/L

Standard: 0.1 mol/L ZnSO4

Instruments: METTLER TOLEDO DL67 Printer EPSON LX400 METTLER TOLEDO ST20A

Method: BL65


Indication: DP660 Phototrode at sensor 2 with 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


1/1 1.0 mL Fixed volume U R1 = 24.06 g/L Cadmium 1/2 1.0 mL Fixed volume U R1 = 23.08 g/L Cadmium 1/3 1.0 mL Fixed volume U R1 = 24.04 g/L Cadmium STATISTICS Number results R1 n = 3 Mean value x = 23.73 g/L Cadmium Standard deviation s = 0.560119 g/L Cadmium Rel. standard deviation srel = 2.361 %


Remarks

Sample preparation1) The sample is diluted and then titrated with 0.1

M EDTA. No pH buffer is added, the bath is alka-line.

2) Use a trituration 1:500 murexide: NaCl.

3) Add the indicator before starting analysis. Keep sample free of air bubbles during titration. Air bubbles and undissolved impurities affect with the photometric indication.

4) Adjust the DP660 at 1000 mV in deionised water before starting titration (100% transmission).

Titration

• Cd(II) ions forms complexes with the indicator murexide in alkaline:

Cd 2+ + Murexide - = Cu-Murexid +

• By titration with EDTA, Murexide is diplaced by EDTA and forms a complex with Cd ions in an alkaline, neutral or weakly acid medium:

Cd 2+ + H2-EDTA2- = Cd-EDTA2- + 2 H+

DisposalClassify as special waste (heavy metals)

Method

Authors: Application Laboratory MT-Germany


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

Title Method ID . . . . . . . . . . . . . BL65 Title . . . . . . . . . . . . . . . Cadmium im alk. Elektrolyt Date/time . . . . . . . . . . . . . 21-02-1994 9:48Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 1.0 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 112.40 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DP660 Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . mL Volume [mL] . . . . . . . . 0.5 Titrant addition . . . . . . . . DYN dE(set) [mV] . . . . . . . . . 8.0 Limits dV . . . . . . . . . . Absolute dV(min) [mL] . . . . . . . 0.05 dV(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU dE [mV] . . . . . . . . . . . 0.5 dt [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . AsymmetricRinse Auxiliary reagent . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . . . . 10.0Calculation Result name . . . . . . . . . . . . Cadmium Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C1=M/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

E-V curve

Application note:Determination of Cd in a Cd-Ag alloySample: 1.5 g Cd-Ag Alloy

Preparation: Add 20 mL HNO3 , boil to dissolve , cool to room temperature, fill up to 100 mL with deionized water. To aliquots of 5 mL add 10 mL buffer ph 4.5 solution and 5 drops HgEDTA

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

METTLER TOLEDO


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

Sample: Chromium (VI) bath, 0.1 mL (diluted/aliquot, see sample prepa-ration)

Substance: Cr(VI) as CrO3 M = 99.99 ; z = 3

Preparation: - 50 mL deionized water - Sulfuric acid 1:1, 10 mL

- Potassium iodide, KI, 1.5 g

Titrant: Sodium thiosulphate, Na2S2O3 c(Na2S2O3)=0.1 mol/L

Standard: Potassium iodate, KIO3

Instruments: METTLER TOLEDO DL70 METTLER TOLEDO ST20A METTLER TOLEDO AT261

Printer EPSON FX850 with serial interface

Method: vd03

Accessories: Titration beakers ME-101974 Peristaltic pump SP40

Indication: DM140 at sensor 2

Results: METTLER DL70 Titrator

vd03 Chromium (VI) measured 23-Nov-1989 12:32 23-Nov-1989 12:04 Titrator Mettler TielSW 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 Na

2S2O3 DM140-SC EQP DYN EQU

Calculation R=Q*C/U C=M/z g/L Rinse H

2O 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 Number results R1 n = 8 Mean value x = 150.24 g/L CrO

3

Standard deviation s = 0.565 g/L CrO3

Rel. standard deviation srel = 0.376 %


RemarksSample preparation1) 1 mL chromium bath is diluted with deionized wa-

ter to 10 mL. 1 mL aliquot corresponds to 0.1 mL original sample.

2) 1 mL aliquot is diluted with 20 mL deion. water. 3) 10 mL sulfuric acid 1:1 are added.4) Add 1.5 g potassium iodide (KI) and cover the bea-

kers to avoid loss of iodine.5) The sample solution is kept in the dark during 5-10

minutes.6) During this time, Cr(VI) is reduced by excess io-

dide (I-) to Cr(III): 2 Cr6+ + 6 I - → 2 Cr3+ + 3 I2 (z = 3) The amount of iodine I2 formed is proportional to

the Cr(VI) content. Titration of iodineThe formed I2 is then titrated with Na2S2O3:

2 S2O32- + I2 → S4O6

2- + 2 I-

• Stir moderately to avoid loss of I2

Method

Author: Joop van den Ouweland, Mettler-Toledo NL

Application note:Cr(VI) in etching solutions

A DP550 Phototrode with starch solution as an indica-tor can be used instead of a DM140 electrode if the solution is clear enough.Sample preparation:See above. In addition, 1 g NH4HF2 is added as a mask-ing agent for Al.(Literature: DL40 Application no. 306)

DisposalSpecial waste

Other titratorsDL50 Graphix, DL53/DL55, DL77.

Method vd03 Chromium (VI) in Cr-bath Version 23-Nov-1989 12:04

Title Method ID . . . . . . . . . . . . . vd03 Title . . . . . . . . . . . . . . . Chromium (VI) in Cr-bath Date/time . . . . . . . . . . . . . 23-Nov-1989 12:04Sample Number samples . . . . . . . . . . . 8 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 0.1 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 99.99 Equivalent number z . . . . . . . . 3Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . Na

2S2O3

Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EP Predispensing . . . . . . . . . mL Volume [mL] . . . . . . . . . 2.0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V [mL] . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 300.0 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . CrO

3

Formula . . . . . . . . . . . . . . R=Q*C/U Constant . . . . . . . . . . . . . . C=M/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Rinse Auxiliary reagent . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . . . . 10.0Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Short-form method . . . . . . . . . Yes Results last sample . . . . . . . . Yes All results . . . . . . . . . . . . Yes Table of measured values . . . . . . Yes E - V curve . . . . . . . . . . . . Yes

E-V curve:


E1 0.000 298.6 0:03 1.143 1.143 296.6 -2.0 -1.8 0:09 1.714 0.571 295.1 -1.5 -2.5 0:14 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 2.600 0.200 291.4 -1.0 -5.2 0:35 2.800 0.200 290.2 -1.2 -6.2 0:40 3.000 0.200 288.7 -1.4 -7.1 0:45 3.200 0.200 287.3 -1.5 -7.3 0:50 3.400 0.200 285.2 -2.1 -10.5 0:54 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 4.446 0.079 243.5 -13.9 -176.5 1.22 4.474 0.028 227.5 -15.9 -569.5 1:29 EQP1 4.494 0.020 190.7 -36.8 -1840.2 1:43 4.514 0.020 168.6 -22.2 -1108.1 1:53 4.535 0.021 160.8 -7.8 -371.3 2:01

Table of measured values:

METTLER TOLEDO


M186 Determination of Cr(III) by back-titration in an electroplating bath

Sample: Chromium (III) bath, 5 mL

Substance: Cr(III) as Cr2O3 M = 151.99 ; z = 3

Preparation: - 10 mL nitric acid 1:1 - 50 mL 0.05 mol/L acid cerium sulphate solution

- 5 min. heating, 50°C

Titrant: Sodium nitrite, NaNO2 c(1/2 NaNO2) = 0.2 mol/L

Standard: For cerium sulphate (see M543): Di-sodium oxalate, C2Na2O4 For sodium nitrite (see M544): Sulphanilic acid, C6H7NO3S

Instruments: METTLER TOLEDO DL55 METTLER TOLEDO ST20A

Printer EPSON LX400

Method: 40003


1 burette DV1020

Indication: DM140

Results:

Sample Cr2O3 content Comments Cr bath (g/L)

n = 2

x 4.2782 VEQ: 10.527 mL srel -- DL40 Appl. no. 308


Author: P. Rast, MT Switzerland



Remarks

• The method was developed on the DL40 titrator (see DL40 applications No. 308) and has been adapted for the DL5x- and DL7x-titrators.

• The Cr(III) content is expressed as Cr2O3 and is detemined by back titration after addition of excess cerium sulphate solution.

Sample preparation1) Add 10 mL nitric acid 1:1 to 5 mL chromium bath

in a glass beaker.

2) 50 mL acid cerium sulphate solution c(Ce(SO4)2 = 0.05 mol/L) are added by using the dispensing function of the titrator. This corresponds to 2.5 mmol/L equivalent Ce(IV)

3) The sample solution is heated during 5 minutes at 50°C. During this time, Cr(III) is oxidized by ex-cess Ce (IV) to Cr(VI):

3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+ (z = 3)

whereas Ce(IV) is reduced to Ce(III):

Ce4+ → Ce3+ + e-

Procedure

1) A Ce(IV)-blank is determined using a similar meth-od as for the determination of Cr(III). The blank value is stored as auxiliary value H2 (mmol).

2) Cr(III) is then determined by a back-titration of excess Ce(IV) using sodium nitrite as a titrant:

2Ce4+ + NO2- + Η2Ο → 2Ce3+ + NO3

- + 2Η+

(z =2)

Chemicals

• 0.05 mol/L acidic cerium sulphate solution: Either 20.22 g Ce(SO4)2•4H2O or 31.63 g Ce(NH4)4(SO4)4• 2H2O are dissolved in 500 mL 1 mol/L sulphuric acid in a 1 L flask. Heat it p to 70°C in a water bath. After cooling to room temperature, fill to the mark with deionized water.

Literature

• DL40 application no. 308, 1985• Applications M543 and M544, in Application

brochure No. 18., "Standardization of Titrants",

MethodMethod 40003 Cr(III) as Cr2O3 Version 16/01/2001 10:10

Title Method ID . . . . . . . . . . . . . 40003 Title . . . . . . . . . . . . . Cr(III) as Cr

2O3

Date/time . . . . . . . . . . . . . 16/01/2001 10:10Sample Sample ID . . . . . . . . . . . . . Cr

2O3

Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 152 Equivalent number z . . . . . . . . 3 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . H

2O

Volume . . . . . . . . . . . 10.0 Conditioning . . . . . . . . . . No Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/2 NaNO

2 Concentration [mol/L] . . . . . . 0.2 Sensor . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 2.0 Wait time [s] . . . . . . . . . . 0 Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 300 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=(H2-Q)*C/m Constant . . . . . . . . . . . . . . C=M/(2*z) Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Cr

2O3

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . Cr

2O3

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Titrant cons. Statistics . . . . . . . . . . . . . YesReport 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

METTLER TOLEDO


M187 Chromium and vanadium in a K2Cr2O7 / V2O5 mixture

Sample: Aqueous acid solution of K2Cr2O7 and V2O5 , 25 mL

Substance: Cr(VI) as K2Cr2O7 (M = 294.19 ; z = 6)

V(V) as V2O5 (M = 181.88 ; z = 2)

Preparation: See next page (Remarks)

Titrant: Fe(NH4)2(SO4)2 • 6H2O (FAS): M = 392.14 c(FAS) = 0.1 mol/L

Standard: Potassium dichromate, K2Cr2O7 (see application M548)

Instruments: METTLER TOLEDO DL53 Epson matrix printer LX800

with serial inteface 8148

Method: 25001


Indication: DM140

Results:

K2Cr2O7 + V2O5 n srel K2Cr2O7 V2O5 n srel Content (mmol) 0.86956 5 0.318 0.6195 0.25008 4 0.2079aliquot

Total content (g) 0.3037 0.2274(10 x aliquot)

Theoreticalcontent (g) 0.3067 0.232

Recovery rate (%) 99.020 98.01

Reactions

1) 1st FAS titration: 1.1 6 Fe2+ + Cr2O7

2- + 14 H+ → 6 Fe3+ + 2 Cr3+ + 7 H2O where Cr2O7

2- + 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


Author: Maria José Schmid




(see DL25 appl. no. 21) and has been adapted for the DL5x- and DL7x-titrators.

• The sample is dissolved in sulphuric acid. It is oxidized with KMnO4 to ensure that chromium and vanadium are present in their highest oxidation state. The first titration with FAS gives the sum of Cr and V in mmol. Iron (Fe(II)) reduces Cr(VI) to Cr(III), while vanadium(V) is reduced to V(IV).

In a second step , V(IV) is again oxidized by KMnO4 to V5+ and titrated with FAS. The difference between the first and the second FAS titration accounts for the chromium content.

Sample preparation1) 0.5 g of sample are heated in 30 mL 10% sulph-

uric acid until complete dissolution.2) In a 250 mL flask dilute with deionized water.3) Take 25 mL aliquots and add KMnO4 solution

dropwise (KMnO4: 5g/100mL). 4) Add 5 mL conc. HCl to eliminate excess

KMnO4 present in the solution.5) Heat until violet permanganate colour disap-

pears, and cool to room temperature.6) 1st titration with FAS (V2O5 + K2Cr2O7).7) Add again KMnO4 until violet is persistent.8) Excess KMnO4 is eliminated by adding KNO2

solution dropwise (KNO2 = 1g/100 mL).9) Add 0.5 g urea to eliminate excess KNO2.10) 2nd titration with FAS (V2O5).11) The difference between first and second result

gives the chromium content.

Chemicals• 0.1 M Fe(NH4)2(SO4)2 • 6H2O (M=392.14):

Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000 mL flask with 10% sulphuric acid and fill to the mark with deionized water.

Literature• DL25 application no. 21, in DL25 Application

Brochure "Chemicals", ME-51724629 (1994).• Application no. M548 and M544, in Applica-

tion brochure 18, "Standardization of Titrants", 2000.

• "Metallurgische Analysen", József Mika, Buda-pest

• "Handbuch für das Eisenhüttenlaboratorium", 2. Band, Chemikerausschuss des Vereins Deutscher Eisenhüttenleute.

MethodMethod 25001 Cr/V Version 16/01/2001 15:30

Title Method ID . . . . . . . . . . . . . 25001 Title . . . . . . . . . . . . . Cr/V Date/time . . . . . . . . . . . . . 16/01/2001 15:30Sample Sample ID . . . . . . . . . . . . . K

2Cr

2O7/V

2O5

Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 25.0 Molar mass M . . . . . . . . . . . . 294.26 Equivalent number z . . . . . . . . 6 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . FAS Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 2.0 Wait time [s] . . . . . . . . . . 15 Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 4.0 ∆V(min) [mL] . . . . . . . . . . 0.1 ∆V(min) . . . . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 5 Result unit . . . . . . . . . . . . mmol Result name . . . . . . . . . . . . K

2Cr

2O7/V

2O5

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Titrant cons. Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


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

Sample: Cr-electroplating bath, 0.2 mL

Substance: Cr(VI) M = 99.99 ; z = 3

Preparation: 50 mL deionized water

Titrant: Fe(NH4)2(SO4)2 • 6H2O (FAS): M = 392.14, c(FAS) = 0.1 mol/L

Standard: Potassium dichromate, K2Cr2O7 (see application M548)

Instruments: METTLER TOLEDO DL50 Printer HP DeskJet 500

Method: 02


Indication: DM140

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 R1 = 320.55 g/L Chroomzuur 3 CrHe128/11 0.2 mL R1 = 320.10 g/L Chroomzuur STATISTICS Number results R1 n = 3 Mean value x = 320.32 g/L Chroomzuur Standard deviation s = 0.22772 g/L Chroomzuur Rel. standard deviation srel = 0.071 %


Author: F. Saes, MT-NL/ W. Jongen


Other titratorsDL53, DL58, DL70ES, DL77.

Remarks

• Cr(VI) is reduced to Cr(III) by the addition of ti-trant: Fe(II) is oxidized to Fe(III) according to:

3 Fe2+ + Cr6+ = 3 Fe3+ + Cr3+

Chemicals

• Fe(NH4)2(SO4)2 • 6H2O (FAS), 0.1 mol/L:

Dissolve 39.21 g Fe(NH4)2(SO4)2•6H2O in a 1000 mL flask with 10% sulphuric acid and fill to the mark with deionized water.

Literature

• Application no. M548 in Application brochure18, "Standardization of Titrants", 2000.

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

Title Method ID . . . . . . . . . . . . . 02 Title . . . . . . . . . . . . . Chroom(VI)-bep in Cr-baden Date/time . . . . . . . . . . . . . 03-11-2000 10:58Sample Sample ID . . . . . . . . . . . . . CrHe128/11 Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 0.2 Molar mass M . . . . . . . . . . . . 99.99 Equivalent number z . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 30 Time [s] . . . . . . . . . . . . . . 15 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . (NH

4)2Fe(SO

4)2

Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 17 Wait time [s] . . . . . . . . . . 60 Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 4.0 ∆V(min) [mL] . . . . . . . . . . 0.05 ∆V(max) [mL] . . . . . . . . . . 0.08 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . . 20.0 Recognition Threshold . . . . . . . . . . . . 300 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 25.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Chroomzuur Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport Output . . . . . . . . . . . . . . . Printer+Computer 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

Table of measured values: Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s

ET1 0.0000 979.0 0:03 9.7140 9.7140 973.2 -5.8 -0.6 0:26 14.5710 4.8570 975.1 1.9 0.4 1:09 ET2 17.0000 2.4290 984.4 9.2 3.8 2:16 17.0800 0.0800 984.2 -0.2 -2.4 2:19 17.1600 0.0800 984.2 0.0 0.0 2:23 17.2400 0.0800 984.2 0.1 0.8 0:26 17.3200 0.0800 984.5 0.3 3.2 2:30 17.4000 0.0800 984.5 0.0 0.0 2:33 17.4800 0.0800 985.1 0.6 7.3 2:36 17.5600 0.0800 985.1 0.1 0.8 2.40 17.6400 0.0800 985.6 0.5 0.5 2:44 17.7200 0.0800 986.1 0.5 6.5 2:49 17.8000 0.0800 986.2 0.1 1.6 2:53 17.8800 0.0800 986.8 0.5 6.5 2:57

19.7200 0.0800 987.6 -2.5 -31.5 5:33 19.8000 0.0800 967.2 -20.4 -254.4 5:54 19.8500 0.0500 960.1 -7.1 -142.2 6:14 19.9300 0.0800 866.5 -93.6 -1170.4 6:35 EQP1 19.9800 0.0500 596.5 -270.0 -5399.8 6:41 20.0300 0.0500 575.8 -20.7 -413.6 7:12 20.0800 0.0500 564.9 -10.9 -218.4 7:15

E-V curve:

METTLER TOLEDO


M189 Determination of free cyanide in a copper bath

Sample: Copper bath, aliquots of 1 mL from diluted solution of 10 mL in 100 mL.

Substance: Free cyanide, CN-

M = 26.02, z = 1

Preparation: 5 mL potassium iodide, KI, 10% 40 mL deion. water

Titrant: Silver nitrate, AgNO3 c(1/2 AgNO3) = 0.2 mol/L

Standard: Sodium chloride (see application M525)

Instruments: METTLER TOLEDO DL53 Matrix printer Epson LX800

with serial inteface 8148 AT261

Method: 25003


Indication: DP550 Phototrode with DIN-Lemo Adapter ME-89600

Results:

CN- n Comments

Mean value 26.84 g/kg 6 DL25 application note in

Standard 0.346 g/kg DL25 Application brochuredeviation s "Petroleum products and electroplating" ME-51 724 627Rel. standard 1.29 %deviation srel


Author: R. Böhlen, MT Switzerland

DisposalCyanide waste


Remarks• The cyanid content determination in e.g. brass

electroplating bath is very important to achieve optimum plating efficiency.

• The method was developed on the DL25 titrator and has been adapted for the DL5x-/DL7x-titrators.

Sample preparation1) 10 mL copper bath are diluted to 100 mL with

deionized water.2) 1 mL aliquot is poured in the titration beaker.3) Add 5 mL 10% potassium iodide solution (KI). 4) 40 mL deionized water is added to the sample.

Reaction• A soluble complex Ag(CN)2

- is first formed by the reaction between silver and cyanide ion:

Ag+ + 2 CN- = Ag(CN)2 -

As long as free cyanide is still present, the solu-tion remains clear, but the first excess of silver causes formation of a white solid that mark the endpoint:

Ag+ + Ag(CN)2- = Ag[Ag(CN)2]

• To obtain a accurate determination of the end-point, potassium iodide is used as an indicator.

During titration, any silver iodide which would tend to form will be kept in solution by the excess of cyanide ion always present until the equiva-lence point is reached:

AgI + 2 CN- = [Ag(CN)2] - + I-

• After the equivalence point, the formation of yel-low silver iodide will lead to a turbidity increase which indicates the end point.

Chemicals

• 10% Potassium iodide, KI: 50 g KI and 50 g NaOH are dissolved in deionized water, and di-luted to 500 mL in a volumetric flask.

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-lytical Chemistry", Holt, Rinehart, and Winston, 1969.

• Application no. M525 in Application brochure18,

MethodMethod 25003 Free CN- in Cu bath Version 17-01-2001 10:50

Title Method ID . . . . . . . . . . . . . 25003 Title . . . . . . . . . . . . . Free CN- in Cu bath Date/time . . . . . . . . . . . . . 17-01-2001 10:50Sample Sample ID . . . . . . . . . . . . . Cu bath Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 26.01 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/2 AgNO

3 Concentration [mol/L] . . . . . . 0.2 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 1.5 Wait time [s] . . . . . . . . . . 20 Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 4.0 ∆V(min) [mL] . . . . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Sample content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=R1*10 Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Bath content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=Q*C3 Constant . . . . . . . . . . . . . . C3=M*1000/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg Result name . . . . . . . . . . . . CN in sample Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M190 Determination of free cyanide in a cyanidic zinc bath

Sample: Cyanidic zinc bath, aliquots of 1 mL

Substance: Free cyanide, CN- M = 26.02, z = 1

Preparation: 40 mL deionized water 5 mL 20% NaOH (5 mol/L)

Titrant: Silver nitrate, AgNO3 c(1/2 AgNO3) = 0.2 mol/L




Method: 40004


Indication: DM141

Results:

CN- n Comments

Mean value 50.994 g/L 5 DL40 application no. 168 as NaCN, M=49 Rel. standard 0.37 %deviation srel





and has been adapted for the DL5x- and DL7x-titrators.

Sample preparation1) 1 mL zinc bath are diluted in a titration beaker

by adding 40 mL deionized water.2) 5 mL 20% NaOH solution are added.

Reaction• The following equation describes the interde-

pendence of the different ions in a zinc bath:

Na2Zn(CN)4 + 4NaOH = Na2ZnO2 + 4NaCN + 2H2O

If excess sodium hydroxide is added, then all cyanide is set free, and can be precipitated by silver ions Ag+ added during titration:

Ag+ + 2 CN- = [Ag(CN)2] -

Note that silver forms in a first step the soluble complex Ag(CN)2

- . As long as free cyanide is still present, the solution remains clear, but the first excess of silver causes formation of a white solid that mark the endpoint:


• The indication with the DM141 combined silver electrode is superior to the traditional turbidi-metric indication with potassium iodide.

• The Zn content analysis is described in M191.

LIterature • DL40 application no. 168 • Vogel's textbook of quantitative inorganic analy-

sis, 4th ed., Longman Group Limited , 1978.• Application no. M525 in Application brochure18,

"Standardization of Titrants", 2000.

MethodMethod 40004 Free CN- in Zn bath Version 18-01-2001 10:13

Title Method ID . . . . . . . . . . . . . 40004 Title . . . . . . . . . . . . . Free CN- in Zn bath Date/time . . . . . . . . . . . . . 18-01-2001 10:13Sample Sample ID . . . . . . . . . . . . . Zn bath Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 26.01 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/2 AgNO

3 Concentration [mol/L] . . . . . . 0.2 Sensor . . . . . . . . . . . . . DM141 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 1.0 Wait time [s] . . . . . . . . . . 10 Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 8.0 ∆V(min) [mL] . . . . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 300 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 15.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Bath content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q*C2 Constant . . . . . . . . . . . . . . C2=M*1000/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg Result name . . . . . . . . . . . . CN in sample Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

Authors: U. Büchi / P. Schauwecker

E-V curve (DL40 application):

METTLER TOLEDO


M191 Back-titration of zinc in a cyanidic zinc bath

Sample: Cyanidic zinc bath, aliquots of 1 mL

Substance: Zn2+

M = 65.37, z = 1

Preparation: 50 mL deionized water 5 mL buffer solution pH 10 5 mL 37-40% formaldehyde sol.

Titrant 1: EDTA, c(EDTA) = 0.1 mol/L

Titrant 2: Zinc sulphate, ZnSO4 c(ZnSO4) = 0.1 mol/L

Standard: For EDTA: Zinc sulphate, ZnSO4 (see appl. M528) For ZnSO4: EDTA

(see appl. M539)



Method: 40005

Accessories: Titration beakers ME-101974 1 additional burette drive DV90 1 additional burette DV1005

(for ZnSO4)

Indication: DP550 Phototrode with DIN-Lemo adapter ME-89600 0.5 mL Erio T, 0.1% solution.

Results:

Zn2+ n Comments

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

Rel. standard 0.08 %deviation srel


Authors: U. Büchi / P. Schauwecker




• Adjust the DP 550 at 1000 mV in deionised water before starting titration (100% transmission).

Sample preparation

1) 1 mL zinc bath are diluted in a titration beaker by adding 50 mL deionized water.

2) 5 mL buffer solution pH 10 are added3) 5 mL 37-40% formaldehyde solution are added.4) 0.5 mL indicator solution are added before titra-

tion.

Reaction

• Zn is determined by back titration after addition of an excess of EDTA (6 mL).

1. Zn(II) ions form complexes with EDTA:

Zn 2+ + H2-EDTA2- = Zn-EDTA2- + 2 H+

2. EDTA excess is titrated with 0.1 mol/L zinc sul-phate solution according to the above reaction.

3. The colour change of Erio T in alkaline medi-

um will be from blue to red when EDTA is titrated with Zn(II).

Chemicals

• Buffer solution pH 10: 70 g ammonium chloride, NH4Cl, and 570 mL

ammonium hydroxide, NH4OH, are dissolved in 1000 mL volumetric flask. Diluto to the mark with deionized water.

Literature

• DL40 application no. 175• Applications no. M528 and 538 in Applica-

tion brochure18, "Standardization of Titrants", 2000.

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

MethodMethod 40005 Zn in Zn bath Version 18-01-2001 10:30

Title Method ID . . . . . . . . . . . . . 40005 Title . . . . . . . . . . . . . Zn in Zn bath Date/time . . . . . . . . . . . . . 18-01-2001 10:30Sample Sample ID . . . . . . . . . . . . . Zn bath Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 65.37 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualDispense Titrant . . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . . 0.1 Volume [mL] . . . . . . . . . . . . 6.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 20 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . ZnSO

4 Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . to volume Volume [mL] . . . . . . . . . . . 2.5 Wait time [s] . . . . . . . . . . 10 Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.02 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.2 ∆t [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 1000 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=(QDISP-Q)*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Bath content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=R1*C2 Constant . . . . . . . . . . . . . . C2=M*1000/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg Result name . . . . . . . . . . . . Zn in sample Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


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

Sample: Standard solution, KAu(CN)2 5 mL aliquots

Substance: Au3+

M = 196.97, z = 1

Preparation: 50 mL deionized water Adjust to pH 3-5 with HNO3.

Titrant: Silver nitrate, AgNO3 c(AgNO3) = 0.1 mol/L




Method: 40005


Indication: DM141

Results:

Au3+ n Comments

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

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

content in 250 mL deionized water M(KAu(CN)

2) = 288.07



Authors: MT Analytical, Application laboratory

DisposalSpecial waste. CAUTION: cyanide is toxic!




Sample preparation1) 5mL standard solution are diluted in a titration

beaker by adding 50 mL deionized water.2) Adjust to pH 3-5 by carefully adding 1 mol/L

nitric acid (or more concentrated, if necessary). CAUTION:

If the pH is lowered below pH 3, then HCN is formed, which is extremely toxic! Therefore work in a fume hood.

Reaction• Gold is precipitated as AgAu(CN)2 during titra-

tion with silver nitrate:

Ag + + Au(CN)2- = AgAu(CN)2

Nitric acid is added to increase the steepness of

the potential jump at the equivalence point.

• If the standard solution should contain chloride, then the latter can be determined by continuing the analysis until a second equivalence point is found. This is due to the precipitation of silver chloride in the sample solution.

• Gold electroplating baths contain free cyanide. Interference from free cyanide can be avoided by adjusting the pH to 5-6 using 30-40% form-aldehyde solution. After a waiting time of 15-20 minutes, the titration can be started.

Literature

• DL40 application no. 8121, 1982.



MethodMethod 40005 Au(III) Version 18-01-2001 16:30

Title Method ID . . . . . . . . . . . . . 40005 Title . . . . . . . . . . . . . Zn in Zn bath Date/time . . . . . . . . . . . . . 18-01-2001 16:30Sample Sample ID . . . . . . . . . . . . . Au-solution Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 196.97 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . AgNO

3 Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DM141 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 8.0 ∆V(min) [mL] . . . . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 800 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 10.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Au content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


Sample: Various gold alloys 0.02 - 0.08 g Compound: Gold, Au M = 196.97; z = 3 Preparation: Solvent mixture conc. HCl: 5 mL / conc. HNO3: 1.5 mL HCl 0.1 mol/L: 40 mL

Titrant 1: Hydroquinone c(1/2 C6H6O2) = 0.05 mol/L

Titrant 2: Cerium(IV) sulfate c(Ce(SO4)2) = 0.01 mol/L

Standard: Pure gold

Instruments: - METTLER TOLEDO DL70ES/77 - METTLER balance AT261 - Printer: HP Deskjet

Method: - gold, test - cer, hydr (standardization)

Accessories: - Two burette drives DV90 - Two 10 mL burettes DV910 - Glass beaker ME-101446 - Pump ME-65241 - Ultrasonic bath

Indication: - DM140-SC at Sensor 2

M208 Determination of gold by precipitation reaction with hydroquinone

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 To determine pure gold or its content in alloys we have chosen the precipitation method with hydroquinone. Most of the associated metals do not interfere with the determination. As the precipitation of gold is too slow to execute a direct titration with hydroquinone, an excess of hydroquinone is added to the dissolved gold. The excess is titrated back with cerium sulfate. Three indivi-dual methods are necessary for the gold determination:• The cer method is used for the factor determination

of cerium sulfate vs. hydroquinone.• The hydr method is used for the standardization of

these two titrants with pure gold.• The gold method is used for the determination of

pure gold or its content in alloys.If the gold content is unknown, the test method is used.

The following points indicate that these methods are suitable for the gold determination:• The titration of hydroquinone with cerium sulfate

is reproducible (see cer method).• It has been shown that gold solutions are very stable

over several days when kept at low pH in hydrochloric acid (Ref. 1).

• It has been shown that copper, iron, zinc, nickel, platinum and palladium do not interfere (Ref. 2). We have found that also silver does not interfere.

Accuracy

The accuracy which can be obtained by these methods depends on- the quality of weighing.- the care with which the gold sample is prepared and

dissolved.- the amount of gold taken.- the precision of titration.

Maintenance of the ElectrodeWe recommend to always clean the electrode after 6 gold titrations because gold contaminates the platinum ring by forming a thin layer:– Place it for two minutes in aqua regia and rinse thor-

oughly with deion. H2O. (See also leaflet of the DM140-SC).

Titration Time of one Sample

Method cer hydr gold test

Time [min] 6 10 10-15 20-25

Chemistry and Calculations1. Gold (Au) is oxidized to the Au3+ ion by aqua re-

gia.2. Au3+ is reduced by an excess of hydroquinone: Au precipitates and quinone is formed

3. The excess of hydroquinone is then oxidized by cerium sulfate (back titration):

mmol C6H6O2 dispensed (excess)

VDISP ∗ c(1/2 C6H6O2) ∗ t

mmol Au mmol Ce(SO4)2 titrated

1/3 Au3+ VEQ ∗ c(Ce(SO4)2 ∗ t

mmol Au =

[VDISP ∗ c(1/2 C6H6O2) ∗ t - VEQ ∗ c(Ce(SO4)2 ∗ t]

VDISP = dispensed hydroquinone [mL]

c(1/2 C6H6O2) = hydroquinone concentration [mol/L]

VEQ = Ce(SO4)2 consumption back titrat. [mL]

c(Ce(SO4)2) = cerium sulfate concentration [mol/L]

DisposalHCl/HNO3: Neutralization with NaOHHydroquinone: Evaporate solution, special waste. Cerium: Precipitate with NaOH and filtrate it,

special waste.Gold: Filtrate solution, special waste.Other metals: Evaporate titrated or filtrated gold

solution. Classify as special waste.

References1. A. Chow, The Stability of Gold Solutions, Talanta 18 (1971),

453-456.

2. S. C. Soundar Rajan and N. Appala Raju, Titrimetic Determination of Gold by Precipitation with Hydroquinone, Talanta 22 (1975), 185-189.

O

2 Au + 6H+ + 3

O

pH ~ 1

6e-

2 Au3+ + 3 =

2e-+ 2 Ce4+ =

pH ~ 1+ 2 Ce3+ + 2H+

O

O

METTLER TOLEDO


Sample: Hydroquinone solution c(1/2 C6H6O2) = 0.05 mol/L: 1.5 mL Compound: Hydroquinone M = 110.11; z = 2

Preparation: HCl 0.1 mol/L: 40 mL Titrant: Cerium(IV) sulfate c(Ce(SO4)2) = 0.01 mol/L

Results:

Preparation of the Hydroquinone Solution– Dissolve 2.753 g hydroquinone in 900 mL deion.

H2O using a 1 L volumetric flask.– Add 10 mL conc. H2SO4 and fill up to the mark with

deion. H2O.

Preparation of the Cerium(IV) Sulfate Solution

– Weigh in 4.043 g cerium sulfate using a glass beaker and add 500 mL deion. H2O.

– Add 10 mL conc. H2SO4 and stir the solution while heating it to approx. 50 °C until the sulfate is dis-solved.

– Pour the solution into a 1 L volumetric flask and fill up to the mark with deion. H2O.

M209 Titer determination of cerium sulfate vs. hydroquinone

Method cer Factor Ce(SO4)2/C

6H4(OH)

2 02-April-1993 13:35

UserMeasured 02-April-1993 13:38

RESULTS


1/1 C6H6O2 1.5 mL Fixed volume U

R1 = 0.98115 Factor 1/2 C

6H6O2 1.5 mL Fixed volume U

R1 = 0.98202 Factor 1/3 C


R1 = 0.98217 Factor 1/4 C


R1 = 0.98261 Factor

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

AUXILIARY VALUE New value H2 = 0.981989 Factor


Method "cer"Method cer Factor Ce(SO4)2/C6H4(OH)2 Version 02-April-1993 13:35

Title Method ID . . . . . . . . . . . . . cer Title . . . . . . . . . . . . . . . Factor Ce(SO

4)2/C

6H4(OH)

2

Date/time . . . . . . . . . . . . . 02-April-1993 13:35Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 1.5 mL ID1 . . . . . . . . . . . . . . . . C

6H6O2

Molar mass M . . . . . . . . . . . . 110.11 Equivalent number z . . . . . . . . 2 Temperature sensor . . . . . . . . . ManualPump Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L Volume [mL] . . . . . . . . . . . . 40.0Dispense Titrant . . . . . . . . . . . . . . 1/2 C

6H6O2

Concentration . . . . . . . . . . . 0.05 Volume [mL] . . . . . . . . . . . . 1.5Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . Ce(SO

4)2

Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . . DM-140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predespensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 6.3 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V (min) [mL] . . . . . . . 0.01 ∆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 . . . . . . . . . . . . 2000.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Factor Formula . . . . . . . . . . . . . . R=VDISP*0.05/(VEQ*c) Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 5Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesInstruction At least one solution is bad! Please renew! Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . (x<0.9)?(x>1.1)Auxiliary value ID text . . . . . . . . . . . . . . Factor Formula . . . . . . . . . . . . . . H2=xRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . Yes

E-V curve


Remarks

• The cerium sulfate solution is unstable because a precipitation occurs. We recommend to prepare a new solution every 2 days.

• The hydroquinone solution is stable but we recom-mend to prepare a new solution every 10 days.

Calculation• Fixed volume U of hydroquinone = dispensed volume VDISP = 1.5 mL

fce/hy =

• If the mean value x of fce/hy is less than 0.9 or greater than 1.1, then the INSTRUCTION method function is displayed.

• The mean value x of fce/hy is stored as auxiliary value H2. It is used to calculate the titer of cerium sulfate versus gold (see method "hydr").

VDISP * c(1/2 C6H6O2)

VEQ * c(Ce(SO4)2)

Table of measured values Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s ET1 0.0000 432.8 0:30 3.6000 3.6000 455.0 22.2 6.2 0:57 5.4000 1.8000 468.6 13.6 7.5 1:16ET2 6.3000 0.9000 479.6 11.1 12.3 1:31 6.5000 0.2000 482.2 3.1 15.4 1:40 6.7000 0.2000 486.7 4.0 20.2 1:49 6.9000 0.2000 491.3 4.6 23.1 2:04 7.1000 0.2000 498.1 6.8 33.9 2:19 7.2780 0.1780 507.0 8.9 49.9 2:37 7.3990 0.1210 517.1 10.1 83.3 2:54 7.4670 0.0680 525.1 8.1 118.4 3:10 7.5190 0.0520 534.6 9.5 181.7 3:27 7.5510 0.0320 542.5 7.9 247.2 3:44 7.5760 0.0250 551.7 9.2 366.8 4:07 7.5920 0.0160 561.0 9.4 586.2 4:24 7.6020 0.0100 567.9 6.9 686.0 4:41 7.6120 0.0100 578.7 10.9 1085.0 4:58 7.6220 0.0100 595.1 16.3 1630.9 5:18EQP1 7.6320 0.0100 640.9 45.8 4585.0 5:39 7.6420 0.0100 681.5 40.6 4059.8 5:53 7.6520 0.0100 708.5 27.0 2702.0 6:13

METTLER TOLEDO


M210 Standardization of hydroquinone with pure gold

Sample: Pure gold: 0.023 - 0.026 g

Compound: Gold M = 196.97; z = 3 Preparation: Solvent mixture conc. HCl: 5 mL / conc. HNO3: 1.5 mL

HCl 0.1 mol/L: 40 mL



Results:

Method hydr Titer of C6H6O2, Ce(SO

4)2 06-April-1993 13:39

UserMeasured 07-April-1993 13:03

RESULTS


1/1 Gold 0.024295 g Weight m R1 = 4.778 mL R2 = 0.22028 mmol C

6H6O2

R3 = 0.99996 Titer C6H6O2


6H6O2

R3 = 0.99924 Titer C6H6O2


6H6O2

R3 = 0.99788 Titer C6H6O2


6H6O2

R3 = 0.99784 Titer C6H6O2

STATISTICS Number results R3 n = 4 Mean value x = 0.99873 Titer C

6H6O2

Standard deviation s = 0.001046 Titer C6H6O2


TITER Titrant 1/2 C

6H6O2 0.05 mol/L

New titer t = 0.998729

TITER Titrant Ce(SO

4)2 0.01 mol/L

New titer t = 1.006319


Method: hydr




Sample PreparationA careful sample preparation is mandatory for reproducible results.– Weigh in a gold sample of approx. 0.025 g.– Clean it with ethanol and let it dry - use tweezers.– Weigh in this sample with a precision of 0.001 mg

and put it in the glass beaker.– Add 5 mL conc. HCl and 1.5 mL conc. HNO3 (fume

hood). Never use prepared aqua regia (unstable!).– To dissolve the gold place the beaker on a heating

plate (110 to 130 °C). The dissolution time can be reduced by using an

ultra-sonic bath (room temperature).– Evaporate to almost dryness (color changes from

yellow to orange), but never evaporate to complete dryness! This would cause the reduction of gold and give false results!

– Rinse the beaker walls with 5 mL conc. HCl and eva-porate again to eliminate the nitrous compounds.

– Repeat this procedure until no yellow fumes are formed anymore.

– Let the sample cool to room T, then titrate.

Method hydr Titer of C6H6O2, Ce(SO4)2

Version 06-April-1993 13:39Title Method ID . . . . . . . . . . . . . hydr Title . . . . . . . . . . . . . . . Titer of C

6H6O2, Ce(SO

4)2

Date/time . . . . . . . . . . . . . 06-April-1993 13:39Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.023 Upper limit [g] . . . . . . . . . 0.026 ID1 . . . . . . . . . . . . . . . . Gold Molar mass M . . . . . . . . . . . . 196.967 Equivalent number z . . . . . . . . 3 Temperature sensor . . . . . . . . . ManualPump Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L Volume [mL] . . . . . . . . . . . . 40.0Dispense Titrant . . . . . . . . . . . . . . 1/2 C

6H6O2

Concentration . . . . . . . . . . . 0.05 Volume [mL] . . . . . . . . . . . . 1.4*H2+304.6*mStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 180Calculation Result name . . . . . . . . . . . . Formula . . . . . . . . . . . . . . R=VDISP*5/H2-C Constant . . . . . . . . . . . . . . C=m*1523*H2 Result unit . . . . . . . . . . . . mL Decimal places . . . . . . . . . . . 3Titration Titrant . . . . . . . . . . . . . . Ce(SO

4)2

Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predespensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.9*R Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V (min) [mL] . . . . . . . 0.01 ∆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 . . . . . . . . . . . . 1000.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 500 Limit B . . . . . . . . . . . 800 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . C

6H6O2

Formula . . . . . . . . . . . . . . R2=VDISP*0.05 Constant . . . . . . . . . . . . . . Result unit . . . . . . . . . . . . mmol Decimal places . . . . . . . . . . . 5Calculation Result name . . . . . . . . . . . . Titer C

6H6O2

Formula . . . . . . . . . . . . . . R3=C3/(R2-VEQ*c*H2) Constant . . . . . . . . . . . . . . C3=(m*1000*z)/M Result unit . . . . . . . . . . . . Decimal places . . . . . . . . . . . 5Statistics Ri (i=index) . . . . . . . . . . . . 3 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesTiter Titrant . . . . . . . . . . . . . . 1/2 C

6H6O2

Concentration [mol/L] . . . . . . . 0.05 Formula t = . . . . . . . xTiter Titrant . . . . . . . . . . . . . . Ce(SO

4)2

Concentration [mol/L] . . . . . . . 0.01 Formula t = . . . . . . . x*H2Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes Table of values . . . . . . . . . . Yes E - V curve . . . . . . . . . . . . YesAuxiliary value ID text . . . . . . . . . . . . . . Titer of C

6H6O2

Formula . . . . . . . . . . . . . . H3=x

Other titratorsDL70ES, DL77.

DisposalSpecial waste.Authors: MT Analytical, Application laboratory

E-V curve


ET1 0.0000 449.7 0:03 2.5020 2.5020 457.5 7.8 3.1 0:13 3.7530 1.2510 462.6 5.0 4.0 0:21 ET2 4.3800 0.6270 465.8 3.3 5.2 0:27 4.5800 0.2000 467.1 1.3 6.3 0:32 4.7800 0.2000 468.4 1.3 6.7 0:37 4.9800 0.2000 469.8 1.4 7.0 0:42 5.1800 0.2000 471.4 1.6 8.1 0:47 5.3800 0.2000 473.1 1.7 8.4 0:53 5.5800 0.2000 475.2 2.1 10.5 0:58 5.7800 0.2000 477.4 2.2 10.9 1:04 5.9800 0.2000 480.1 2.7 13.7 1:09 6.1800 0.2000 483.6 3.4 17.2 1:15 6.3800 0.2000 488.1 4.6 22.8 1:22 6.5800 0.2000 495.2 7.1 35.3 1:28 6.7460 0.1660 506.4 11.2 67.5 1:37 6.8260 0.0800 520.1 13.7 171.5 1:46 6.8550 0.0290 530.0 9.9 340.3 1:54 6.8700 0.0150 539.9 9.9 662.6 2:03 6.8800 0.0100 548.6 8.7 868.0 2:15 6.8900 0.0100 558.8 10.2 1022.0 2.30 6.9000 0.0100 571.0 12.3 1225.0 2:46 6.9100 0.0100 589.5 18.4 1840.9 3:07 6.9200 0.0100 625.8 36.3 3633.0 3:38EQP1 6.9300 0.0100 679.2 53.4 5340.8 4:08 6.9400 0.0100 703.3 23.1 2408.0 4:30 6.9500 0.0100 712.1 8.8 882.0 4:40

Table of measured values


c. Titer determination of C6H6O2 vs. gold

thy =

The titer of C6H6O2 thy is stored as auxiliary value H3 for further use in the "gold" method.

d. Titer determination of Ce(SO4)2 vs. gold The factor fce/hy was obtained by the standardizati-

on of cerium sulfate with hydroquinone (method "cer"). The titer of cerium sulfate must be referred to gold.

tce = thy * fce/hy = thy * H2

whereVDISP = dispensed volume of hydroquinone

[mL]

VEQ = cerium sulfate consumption by back titration

VEQth = calculated cerium sulfate consumption for back titration

z = equivalent number of gold = 3

m = size of gold sample [g]

M = molar mass of gold = 196.967

c(1/2 C6H6O2)= hydroquinone concentration =

0.05 mol/L

c(Ce(SO4)2 = cerium sulfate concentration =

0.01 mol/L

fce/hy = factor of cerium sulfate vs. hydroquinone (stored as H2)

Reaction TimeThe complete reduction of gold with hydroquinone takes about 2 minutes; thus the stirring time shall not be less than 180 s.

M (VDISP * c(1/2 C6H6O2) – VEQ * c(Ce(SO4)2) * fce/hy)

z * m * 1000

M * c(Ce(SO4)2) * fce/hy

c(1/2 C6H6O2) z * m * 1000

c(Ce(SO4)2)

VDISP

fce/hy

* –

m * 1523 * H2 VDISP/H2 –* 5

Remarks

Calculations

a. Dispensing of hydroquinone An excess of hydroquinone is dispensed depending

on the size of the gold sample. Furthermore, ap-prox. 7 mL of the cerium sulfate titrant should be consumed by the back titration. Thus the dispensed volume of hydro-quinone (VDISP) is calculated in the DISPENSE function.

VDISP = mL hydroquinone + mL hydroquinone reacted with gold back titrated with Ce(SO4)2

The best accuracy is achieved if the consumption of hydroquinone and cerium sulfate is less than 1 burette volume each, i.e. 10 mL. Therefore the sample weight must lie in the range of 0.023 and 0.026 g gold. Also the titer values of both titrants must lie in the range of 0.95 and 1.1.

b. Predispensing of cerium sulfate (back titration) Predispensing is always applied to speed up the

titration. Here a predispensing volume of 90% of the total cerium sulfate consumption (VEQth) is used. This volume is calculated in the first CAL-CULATION function.

VEQth =

VEQth =

M * c(1/2 C6H6O2)z * m * 1000 7 mL * c(Ce(SO4)2) * fce/hy

c(1/2 C6H6O2)+

304.6 * m += 1.4 * H2

=


METTLER TOLEDO


Method gold Purity of gold samples 08-April-1993 8:48UserMeasured 08-April-1993 15:36

RESULTS


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

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

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

AUXILIARY VALUE New VALUE H4 = 0.375

M179 Determination of the gold content in alloy

Sample: Various gold alloys with a known (±10%) gold content 0.02 - 0.08 g Compound: Gold, Au M = 196.97; z = 3 Preparation: Solvent mixture conc. HCl: 5 mL / conc. HNO3: 1.5 mL

HCl 0.1 mol/L: 40 mL




Method: - gold - cer, hydr (standardization)




Method "gold" Remarks

• Before executing this method the carat or percent value of the alloy has to be entered as auxiliary value H1. If the gold content is unknown, use the "test" method (see M180). Enter thy as H3.

• The gold concentration of the sample entered as carat or percent is automatically transformed into the fraction of gold and stored as H4 using the AUXILIARY VALUE functions.

Sample PreparationProceed with the sample preparation as described in method "hydr". The following remarks are impor-tant:• Press alloys as thin as possible using a rolling device

so that the dissolution is easier.• Use an ultrasonic bath especially for silver alloys,

be-cause silver chloride does passivate the gold surface.

• Evaporate the aqua regia solution.• Add 5 mL conc. HCl to the beaker and put it in the

ultrasonic bath for 5 minutes.• Evaporate again.• If it is not yet dissolved, repeat the procedure.• Never evaporate to complete dryness!

Sample Weight (g)

Content (carat) lower limit upper limit

24 0.023 0.026

21 0.026 0.030

18 0.031 0.034

14 0.040 0.044

12 0.046 0.052

9 0.062 0.069

Dispensing of Hydroquinone

• An excess of hydroquinone is dispensed depending on the sample size and the gold concentration.

• Furthermore, the dispensed volume (VDISP) is calculated for a consumption of 6 mL cerium sulfate

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

Title Method ID . . . . . . . . . . . . . gold Title . . . . . . . . . . . . . . . Purity of gold samples Date/time . . . . . . . . . . . . . 08-April-1993 8:48Sample Number samples . . . . . . . . . . . 4 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.02 Upper limit [g] . . . . . . . . . 0.08 ID1 . . . . . . . . . . . . . . . . Gold Molar mass M . . . . . . . . . . . . 196.967 Equivalent number z . . . . . . . . 3 Temperature sensor . . . . . . . . . ManualAuxiliary value ID text . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . . H4=H1/24 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . H1<=24Auxiliary value ID text . . . . . . . . . . . . . . Formula . . . . . . . . . . . . . . H4=H1/100 Condition . . . . . . . . . . . . . Yes Condition . . . . . . . . . . . . (H1>24)!(H1<=100)Pump Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L Volume [mL] . . . . . . . . . . . . 40.0Dispense Titrant . . . . . . . . . . . . . . 1/2 C

6H6O2

Concentration . . . . . . . . . . . 0.05 Volume [mL] . . . . . . . . . . . . 1.2*H2+304.6*m*H4/H3Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 180Titration Titrant . . . . . . . . . . . . . . Ce(SO

4)2

Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . . DM-140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predespensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 2.1 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V (min) [mL] . . . . . . . 0.02 ∆V (max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 400.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 500 Limit B . . . . . . . . . . . 700 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . purity Formula . . . . . . . . . . . . . . R=100*(QDISP-Q)*C Constant . . . . . . . . . . . . . . C=M/(m*z*1000) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 3Calculation Result name . . . . . . . . . . . . purity Formula . . . . . . . . . . . . . . R2=24*(QDISP-Q)*C2 Constant . . . . . . . . . . . . . . C2=M/(m*z*1000) Result unit . . . . . . . . . . . . carat Decimal places . . . . . . . . . . . 3Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesStatistics Ri (i=index) . . . . . . . . . . . . R2 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

= mL hydroquinone + mL hydroquinone back reacted with gold titrated with Ce(SO4)2

M * c(1/2 C6H6O2) * thy

z * m * Aux * 1000=c(1/2 C6H6O2)

6 mL * c(Ce(SO4)2) * fce/hy+

= 304.6 * m * H4/H3 + 1.2 * H2

VDISP =


24 * M * (QDISP – Q)

z * 1000 * m

Calculation of the result

The gold content Au is:

Au = [carat]

whereVDISP = dispensed volume of hydroquinone

[mL]QDISP = dispensed amount of hydroquinone

[mmol]Q = cerium sulfate consumption by back

titration [mmol]z = equivalent number of gold = 3m = size of gold sample [g]M = molar mass of gold = 196.967c(1/2 C6H6O2) = hydroquinone concentrat ion =

0.05 mol/Lc(Ce(SO4)2 = cerium sulfate concentration =

0.01 mol/Lfce/hy = titer of cerium sulfate vs. hydroquinone

(storedas H2)thy = titer of hydroquinone (stored as H3)Aux = presumed gold content (stored as


DisposalSpecial waste.

Other titratorsDL70ES, DL77.

Reaction Time

• The complete reduction of gold with hydroquinone takes about 3 minutes; thus the stirring time shall not be less than 180 s.

Titration Parameters

• The titration curve may show noisy behavior in the range of the equivalence point. This may especially occur with samples of low gold content. In this case we recommend to increase the minimum increment ∆V(min) to >0.02 mL.

METTLER TOLEDO


Sample: Various gold alloys with an unknown gold content: 0.03 - 0.06 g

Method "test"

M180 Determination of the approximate gold content content in alloys

Titration Curve: Back Titration with Cerium Sulfate

RemarksWith this method the gold content can be determined within approx. 3%. The gold method can then be executed to obtain the precise result.

1st TITRATION function: The gold reduction with hydroqui-none is done by a titration in order• to determine the total amount of C6H6O2 dispensed

and• to obtain an excess of at least 1 mL C6H6O2 (titrant

addi-tion ∆V = 0.5 mL).

The total amount of C6H6O2 dispensed is stored as auxiliary value H5.

2nd TITRATION function: The excess of hydroquinone is titrated back with cerium sulfate.

Method test Approximate gold content Version 10-April-1993 11:09

Title Method ID . . . . . . . . . . . . . test Title . . . . . . . . . . . . . . . Approximate gold con-tent Date/time . . . . . . . . . . . . . 10-April-1993 11:09Sample Number samples . . . . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.03 Upper limit [g] . . . . . . . . . 0.06 ID1 . . . . . . . . . . . . . . . . Gold Molar mass M . . . . . . . . . . . . 196.967 Equivalent number z . . . . . . . . 3 Temperature sensor . . . . . . . . . ManualPump Auxiliary reagent . . . . . . . . . HCl 0.1 mol/L Volume [mL] . . . . . . . . . . . . 40.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . 1/2 C

6H6O2

Concentration [mol/L] . . . . . . . 0.05 Sensor . . . . . . . . . . . . . . . DM-140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . INC ∆V [mL] . . . . . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 10.0 t(max) [s] . . . . . . . . . . 40.0 Threshold . . . . . . . . . . . . 200.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 800 Limit B . . . . . . . . . . . 500 Maximum volume [mL] . . . . . . . 20.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardAuxiliary value ID text . . . . . . . . . . . . . . Amount of C

6H6O2

Formula . . . . . . . . . . . . . . H5=Q+QEXStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 120Titration Titrant . . . . . . . . . . . . . . Ce(SO

4)2

Concentration [mol/L] . . . . . . . 0.01 Sensor . . . . . . . . . . . . . . . DM-140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V (min) [mL] . . . . . . . 0.02 ∆V (max) [mL] . . . . . . . 0.2 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 400.0 EQP range . . . . . . . . . . . . Yes Limit A . . . . . . . . . . . 500 Limit B . . . . . . . . . . . 700 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . content Formula . . . . . . . . . . . . . . R=100*(H5-Q[2])*C Constant . . . . . . . . . . . . . . C=M/(m*z*1000) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 1Calculation Result name . . . . . . . . . . . . content Formula . . . . . . . . . . . . . . R2=24*(H5-Q[2])*C2 Constant . . . . . . . . . . . . . . C2=M/(m*z*1000) Result unit . . . . . . . . . . . . carat Decimal places . . . . . . . . . . . 1Record Output unit . . . . . . . . . . . . Printer

Titration Curve: Gold Reduction with Hydroquinone



METTLER TOLEDO


M192 Determination of lead(IV) in batteries

Sample: Lead for batteries (PbO2: 8-30%) 0.5 - 1 g

Substance: Lead, Pb4+ as lead oxide, PbO2 M = 239.2, z = 2

Preparation: 30% HNO3 , 15 mL 10% H2O2 , 5 mL Hot deioniezd water, 30 mL.

Titrant: Potassium permanganate, KMnO4 c(1/5 KMnO4) = 0.1 mol/L

Standard: Di-sodium oxalate, Na2C2O4 (see application M527)



Method: 40006

Accessories: Glass titration beakers ME-101446

Indication: DM140

Results:

PbO2 n Comments Mean value 8.5547 % 5 DL40 application no. 305

Theoretical 8-10 % Sample size: 1 g content Consumption: 20 mL


Mean value 32.64 % 5 DL40 application no. 305

Theoretical 30 ± 3 % Sample size : 0.5 g content Rel. standard 0.48 % Consumption: 12 mLdeviation srel

Mean value 2.84 mmol 4 DL40 application no. 305

Theoretical 0 Blank value content Consumption: 27.5 mL Rel. standard 0.48 %

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 77/100Authors: MT Analytical, Application laboratory





• The Pb(IV) content is expressed as PbO2 and is detemined by back titration after addition of excess hydrogen peroxide solution.

Sample preparation

1) Dissolve the sample in a glass titration beaker by adding 15 mL of 30% nitric acid HNO3. Stir the solution until all red traces are dissolved.

2) 5 mL 10% hydrogen peroxide solution are added by using the dispensing function of the titrator. Pb(IV) is reduced to Pb(II) by H2O2:

Pb4+ + H2O2 = Pb2+ + O2 + 2 H+ (z = 2)

Pb4+ + 2 e- = Pb2+ 3) 30 mL hot deionized water are added and stir to

achieve complete solvation.

Procedure

1) The exact concentration of the H2O2-solution is determined by performing a blank titration using a similar method as for the sample determination. The blank value is stored as auxiliary value H4 (mmol).

2) Pb(IV) is then determined by a back-titration of excess H2O2 using potassium permanganate as a titrant:

2MnO4 - + 5 Η2Ο2 + 6 H+ =

2Mn2+ + 5O2 + 8Η2O (z =2)

Literature

• DL40 application no. 305

MethodMethod 40006 PbO2 Version 19-01-2001 17:32

Title Method ID . . . . . . . . . . . . . 40006 Title . . . . . . . . . . . . . PbO

2 Date/time . . . . . . . . . . . . . 19-01-2001 17:32Sample Sample ID . . . . . . . . . . . . . Lead in batteries Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.5 Upper limit [g] . . . . . . . . . 1.5 Molar mass M . . . . . . . . . . . . 239.2 Equivalent number z . . . . . . . . 2 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/5 KMnO4 Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DM140 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Dynamic ∆E(set) [mV] . . . . . . . . . . 8.0 ∆V(min) [mL] . . . . . . . . . . 0.02 ∆V(max) [mL] . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 2.0 ∆t [s] . . . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 300 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 30.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=(H4-Q)*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . Pb content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M193 Complexometric titration of lead in alloy

Sample: Lead-tin-antimony alloy, 10 mL aliquots

Substance: Lead, Pb2+

M = 207.2, z = 1

Preparation: 50 mL deion. water Titrant: EDTA c(EDTA) = 0.1 mol/L

Standard: Zinc sulphate, ZnSO4 (see application M528)

Instruments: METTLER TOLEDO DL53 Rondo 60 sample changer

Olivetti ArtJet 20

Method: 40007

Accessories: Glass titration beakers ME-101446

Indication: DP550 Phototrode with DIN-Lemo adapter ME-89600

Results:

Pb2+ n Comments Mean value 45.49 % 5 DL40 application no. 406

Consumption: 1.7 mL


Mean value 98.13 % 5 DL40 application no. 403

Test with Pb((NO3)2 standard

Preparation: Rel. standard 0.21 % 1. use buffer solution pH 5.4 deviation srel 2. Indicator: xylenol orange 3. Sensor: DP550 4. Titrant: 0.1 ml/L EDTA

Buffer pH 4.5: Hexamethylene tetramine: 400 g Hydrochloric acid:100 mL Dilute with deion. water to 1 L

Electronics and electroplating applications METTLER TOLEDO DL5x and DL7x Titrators Page 79/100Authors: MT Analytical, Application laboratory





• The Pb(II) content is detemined by complexometric titration with EDTA.

Sample preparation

1) Dissolve 1-1.5 g of the finely pulverized alloy in a 250 mL beaker.

2) Add 20 mL 1:1 HCl and heat3) To the hot solution add 10 mL of 1.1 HNO3, heat

until dissolution is complete. 4) Add 20 mL of 4% KCl, 50 mL of 1.1 HCl, 50 mL

deion. water and 20 mL 20% tartaric acid solu-tion.

5) Boil 2 minutes.6) Cool to room temperature.7) Add 5 drops of 0.2% aqueous solution of xylenol

orange and 30% hexamethylene tetramine until the solution turns red (for this sample size you need about 35 mL).

8) Dilute to 200 mL with 1:1 HCl.9) Take aliquots of 10 mL.

Procedure

1) This procedure is only suitable for the determina-tion of Pb in Pb/Sn/Sb alloy. The alloy is dissolved due to the formation in a strong acid medium of a soluble chloro-plumbate complex.

2) The solution is diluted to volume using 1:1 HCl since no precipitate is formed at high concentration of HCl.

3) Sn and Sb are masked by tartaric acid. Pb can be directly determined by titration with EDTA:

Pb2+ + H2-EDTA2- = Pb-EDTA2- + 2 H+

The colour change at the equivalence point turns from red to yellow.

Literature

• DL40 application no. 406


MethodMethod 40007 Pb2+

Version 22-01-2001 10:47

Title Method ID . . . . . . . . . . . . . 40007 Title . . . . . . . . . . . . . Pb2+

Date/time . . . . . . . . . . . . . 22-01-2001 10:47Sample Sample ID . . . . . . . . . . . . . Pb/Sn/Sb alloy Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 10.0 Molar mass M . . . . . . . . . . . . 207.2 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . ST20A Pump . . . . . . . . . . . . . . No Rinse . . . . . . . . . . . . . . Yes Solvent . . . . . . . . . . . H

2O

Volume . . . . . . . . . . . 20.0 Conditioning . . . . . . . . . . No Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.05

Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 300 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 5.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . Pb content Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 3 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 0 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M194 Determination of nickel in an electroplating bath

Sample: Nickel bath, 0.5 mL

Substance: Nickel as NiSO4, M = 262.7 g/mol, z = 1

Preparation: Deionised water, 50 mL Buffer pH 10, 10 mL

0.5 g Murexide/NaCl 1:200 tritu-ration.

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

Standard: Zinc sulfate, c(ZnSO4) = 0.1 mol/L (See METTLER method M007)

Instruments: METTLER TOLEDO DL70 METTLER TOLEDO ST20A METTLER TOLEDO AT261 Matrix Printer Epson LX800 with serial interface 8148

Method: vd01

Accessories: Titration beakers ME-101974 2 peristaltic pumps ME-65241

Indication: DP550 Phototrode at sensor 2 with DIN-Lemo adapter

ME-89600

Results: vd01 Nickel in Galvanic Bath measured 19-Dec-1989 15:5019-Dec-1989 15:22 Titrator Mettler TielSW Version 1.2 User J.v.d.Ouweland

RESULTS


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

2O

1/2 0.5 mL 82.59 g/L NiSO4.6H

2O

1/3 0.5 mL 82.38 g/L NiSO4.6H

2O

1/4 0.5 mL 82.07 g/L NiSO4.6H

2O

1/5 0.5 mL 82.14 g/L NiSO4.6H

2O

1/6 0.5 mL 82.75 g/L NiSO4.6H

2O

1/7 0.5 mL 82.48 g/L NiSO4.6H

2O

1/8 0.5 mL 82.31 g/L NiSO4.6H

2O

STATISTICS Number results R1 n = 8 Mean value x = 82.39 g/L NiSO

4.6H

2O

Standard deviation s = 0.225 g/L NiSO4.6H

2O

Rel. standard deviation srel = 0.273 %


Remarks• The Ni(II) content is detemined by complexometric

titration with EDTA. Murexide is used as indicator, and the colour change is monitored by a DP550 phototrode.

Sample preparation1) Add the mureide indicator to the sample2) The addition of water and buffer is performed au-

tomatically by two peristaltic pumps.

Procedure

• Nickel ions forms a yellow complex with murexide in alkaline solution:

Ni 2+ + Murexide - → Ni-Murexid+

Ni forms a more stable complex with EDTA:

Ni-Murexid+ + EDTA 4- → Ni-EDTA2-+ Murex-ide-

At the equivalence point, Ni(II) has been com-plexed by EDTA and murexide is free in the alka-line solution. There is a colour change from yellow to blue-violet.

• The shape of the titration curve is somewhat af-fected by the concentration of the indicator. The results, however, do not differ significantly.

Chemicals• Buffer solution pH 10: 570 mL 25% NH3 and

MethodMethod vd01 Nickel in Galvanic Bath Version 13-Sep-1991 15:22

Title Method ID . . . . . . . . . . . . . vd01 Title . . . . . . . . . . . . . Nickel in Galvanic Bath Date/time . . . . . . . . . . . . . 13-Sep-1991 15:22Sample Number samples . . . . . . . . . . 8 Titration stand . . . . . . . . . . ST20 Entry type . . . . . . . . . . . . . Fixed volume U Volume [mL] . . . . . . . . . . . 0.5 ID1 . . . . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 262.7 Equivalent number z . . . . . . . . 1Pump Auxiliary reagent . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . . . . 10.0Pump Auxiliary reagent . . . . . . . . . Buffer 10 Volume [mL] . . . . . . . . . . . . 10.0Stir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10Titration Titrant . . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . DP550 Unit of meas . . . . . . . . . . . . As installed Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . mL Volume [mL] . . . . . . . . . 0.5 Titrant addition . . . . . . . . DYN ∆E(set)[mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) . . . . . . . . . . 0.02 ∆V(max) . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . 10.0 Maximum volume [mL] . . . . . . . 15.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . NiSO

4.6H

2O

Formula . . . . . . . . . . . . . . R=Q*C/U Constant . . . . . . . . . . . . . . C=M/z Result unit . . . . . . . . . . . . g/L Decimal places . . . . . . . . . . . 2Rinse Auxiliary reagent . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . . . . 10.0Statistics Ri (i=index) . . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . YesRecord Short-form method . . . . . . . . . Yes All results . . . . . . . . . . . . Yes Table of measured values . . . . . . Yes E - V curve . . . . . . . . . . . . Yes

Literature1. METTLER TOLEDO DL70 Applications Bro-

chure No. 12. METTLER TOLEDO DL40 Application No. 4033. METTLER TOLEDO Application No. M066,

M528.


Other titratorsDL50 Graphix, DL53/55 (use standard methods)DL58, DL77. Author: J. v.d. Ouweland, MT-NL

Table of mesured values and E-V curve

METTLER TOLEDO


Sample: Silver, silver alloys approx. 0.04 g Compound: Silver, Ag M = 107.868; z = 1 Preparation: Deion. H2O, 50 mL HNO3 33%, 3 mL Titrant: Sodium chloride c(NaCl) = 0.1 mol/L

Standard: Silver nitrate, AgNO3 (see application M536)

Results:

Instruments: METTLER TOLEDO DL70 METTLER TOLEDO microbalance MT5 Printer: EPSON FX800

Method: Ag02

Accessories: Glass titration beaker ME-101446 Indication: DM141-SC at Sensor 2

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

23-04-1990 10:51 TitratorSW Version 1.2 User rvr

RESULTS

No Identification Weight Results

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

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

M195 Determination of silver in silver alloy


Method Remarks

Sample Preparation– Clean the sample with acetone and let it dry – use

tweezers.– Weigh in a sample corresponding to approx. 40 mg

Ag and read to ±0.01 mg; then put it in the beaker.– Add 3 mL of 33% HNO3 and warm up to 60 °C in

a wa-ter bath until the sample is completely dissol-ved.

– Let the sample cool down to room temperature and add 50 mL deion. H2O.

This procedure is prerequisite to achieve high precisi-on.

High PrecisionMethod and preparation are designed for highest preci-sion, i.e. RSD better than 0.050%. Our example shows a reproducibility of 0.018% RSD. This high precision is required, for example, by mint companies or electronic circuitry manufacturers.

High SpeedThe method was also streamlined to fast titrations.

Method AgO2 Purity of AgNO3

Version 23-04-1990 10:51

Title Method ID . . . . . . . . . . . . . AgO2 Title . . . . . . . . . . . . . . . Purity of AgNO

3

Date/time . . . . . . . . . . . . . 23-04-1990 10:51Sample Number samples . . . . . . . . . . . 3 Titration stand . . . . . . . . . . Stand 1 Entry type . . . . . . . . . . . . . Weight m Lower limit [g] . . . . . . . . . 0.03 Upper limit [g] . . . . . . . . . 0.07 ID1 . . . . . . . . . . . . . . . . Ag Alloy Molar mass M . . . . . . . . . . . . 107.868 Equivalent number z . . . . . . . . 1Stir Speed [%] . . . . . . . . . . . . . 60 Time [s] . . . . . . . . . . . . . . 5Titration Titrant . . . . . . . . . . . . . . NaCl Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM-141-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . % nominal content Metered amount [%] . . . . . . 95.0 Nominal content [%] . . . . . 95.0 Conversion const. . . . . . . M/(10*z) Titrant addition . . . . . . . . INC ∆V [mL] . . . . . . . . . . . 0.05 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 15.0 Threshold . . . . . . . . . . . . 500.0 Maximum volume [mL] . . . . . . . 10.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Result name . . . . . . . . . . . . Silver Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Result unit . . . . . . . . . . . . % Decimal places . . . . . . . . . . . 4Record Raw results . . . . . . . . . . . . Yes Table of measured values . . . . . . Yes E - V curve . . . . . . . . . . . . YesStatistics Ri (i 0 index) . . . . . . . . . . . R1 Standard deviation s . . . . . . . . Yes Rel. standard deviation srel . . . . Yes Outlier test . . . . . . . . . . . . YesRecord All results . . . . . . . . . . . . Yes

Literature

3. METTLER TOLEDO Application No. M536 (appl. brochure no. 18).

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

Other titratorsDL50 Graphix, DL53/55 (use standard methods)DL58, DL77.

Table of measured values

E-V curve

Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s E1 0.000 215.9 0:03 2.223 2.223 197.4 -18.5 -8.3 0:13 3.335 1.112 175.0 -22.4 -20.2 0:21E2 3.891 0.556 140.5 -34.5 -62.0 0:29 3.941 0.050 134.7 -5.8 -115.6 0:34 3.991 0.050 126.5 -8.2 -163.5 0:40 4.041 0.050 111.0 -15.5 -309.7 0:46 4.091 0.050 75.6 -35.5 -709.2 0:53EQP1 4.141 0.050 31.0 -44.6 -891.8 0:59 4.191 0.050 15.0 -16.0 -319.5 1:04 4.241 0.050 5.4 -9.6 -192.1 1:10

Author: Ruth von Rotz, Application Laboratory MT

METTLER TOLEDO


M196 Determination of free potassium cyanide in a silver bath

Sample: Copper bath, 1 mL

Substance: Potassium cyanide, KCN M = 65.12, z = 1


Titrant: Silver nitrate, AgNO3 c(AgNO3) = 0.1 mol/L



Matrix printer Epson LX800 with serial inteface 8148

AT261

Method: BL20


Indication: DM141-SC

Results:

Method BL20 KCN im cy.Ag.Bad 17-02-1994 10:46 User Measured 24-02-1994 14:49

RESULTS


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

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


Author: Application laboratory, MT Germany


Other titratorsDL50 Graphix, DL53/DL55/DL58, DL70ES, DL77.

Remarks

Sample preparation

1) 1 mL silver bath is diluted with 50 mL deion-ized water

Reaction

• A soluble complex Ag(CN)2 - is first formed by

the reaction between silver and cyanide ion: Ag+ + 2 CN- = Ag(CN)2

-

As long as free cyanide is still present, the solu-tion remains clear, but the first excess of silver causes formation of a white solid that mark the endpoint:


• since 1 mol of Ag ions reacts with two moles of cyanides, the factor 2 is taken into account in the calculation.

Method

Literature

• Application note, DL25 Application Brochure "Petroleum and electroplating", ME-51724627.


• D.A. Skoog, D.M. West, "Fundamentals of Ana-lytical Chemistry", Holt, Rinehart, and Winston, 1969.


E-V curve

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

Title Method ID . . . . . . . . . . . . . BL20 Title . . . . . . . . . . . . . KCN im cy.Ag.Bad Date/time . . . . . . . . . . . . . 17-02-1994 10:46Sample Sample no. . . . . . . . . . . . . . 20 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Sample ID . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 65.12 Equivalent number z . . . . . . . . 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant . . . . . . . . . . . . . . AgNO

3 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM141-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . to volume Volume [mL] . . . . . . . . . 1 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Absolute ∆V(min) [mL] . . . . . . . 0.05 ∆V(max) [mL] . . . . . . . 0.5 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 3.0 t(max) [s] . . . . . . . . . . 30.0 Threshold . . . . . . . . . . . . 50.0 Maximum volume [mL] . . . . . . . 30.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardRinse Auxiliary reagent . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . . . . 10.0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M*2 Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . KCN Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Verbrauch Statistics . . . . . . . . . . . . . YesStatistik Ri (i=Index) . . . . . . . . . . . . R1Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

METTLER TOLEDO


M197 Titration of Tin(II) in acidic tin bath

Sample: Acidic tin bath, 2 mL

Substance: Tin(II), Sn2+

M = 118.71, z = 2


Titrant: Iodine, I2 c(1/2 I2) = 0.1 mol/L

Standard: Arsenic trioxide, As2O3 (see application M016)


Matrix printer Epson LX800 with serial inteface 8148

AT261

Method: BL70


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


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

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


Author: Application laboratory, MT Germany

DisposalCAUTION: arsenic trioxide is very poisonous!Special waste

Other titratorsDL50 GraphixDL53/DL55/DL58DL70ES, DL77.

Remarks

Sample preparation

1) 2 mL acidic silver bath is diluted with 50 mL deionized water.

Reaction

• Stannous tin Sn(II) is converted quantitatively into stannic tin Sn(IV) by titration with iodine in the presence of hydrochloric acid:

SnCl2 + 2HCl + I2 = SnCl4 + 2 HI

where

Sn2+ = Sn4+ + 2 e-

I2 + 2 e- = 2 I-

Method

Literature

• Application note, MT Germany, in application brochure "Galvanik", 1995.

• K.E. Langford, J.E. Parker, "Analysis of electro-plating and related solutions", 4th edition, Robert Draper Ltd. , 1971.

• Application no. M016, Application brochure 9, "Standardization of Titrants II" ME-51724652, 1994.

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

Title Method ID . . . . . . . . . . . . . BL70 Title . . . . . . . . . . . . . KCN im cy.Ag.Bad Date/time . . . . . . . . . . . . . 21-02-1994 16:09Sample Sample no. . . . . . . . . . . . . . 20 Titration stand . . . . . . . . . . ST20 1 Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 2.0 Sample ID . . . . . . . . . . . . . Molar mass M . . . . . . . . . . . . 118.71 Equivalent number z . . . . . . . . 2 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 10 EQP titration Titrant . . . . . . . . . . . . . . 1/2 I

2 Concentration [mol/L] . . . . . . . 0.1 Sensor . . . . . . . . . . . . . . . DM140-SC Unit of meas. . . . . . . . . . . . mV Titration mode . . . . . . . . . . . EQP Predispensing 1 . . . . . . . . . to volume Volume [mL] . . . . . . . . . 0 Titrant addition . . . . . . . . DYN ∆E(set) [mV] . . . . . . . . . 8.0 Limits ∆V . . . . . . . . . . Relative ∆V(min) [%dosVol] . . . . . 0.5 ∆V(max) [%buVol] . . . . . 5.0 Measure mode . . . . . . . . . . EQU ∆E [mV] . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . 1.0 t(min) [s] . . . . . . . . . . 2.0 t(max) [s] . . . . . . . . . . 20.0 Threshold . . . . . . . . . . . . 100.0 Maximum volume [mL] . . . . . . . 50.0 Termination after n EQPs . . . . Yes n = . . . . . . . . . . . . . 1 Evaluation procedure . . . . . . StandardCalculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . Sn2+ Statistics . . . . . . . . . . . . . YesRinse Auxiliary reagent . . . . . . . . . H

2O

Volume [mL] . . . . . . . . . . . . 10.0Statistik Ri (i=Index) . . . . . . . . . . . . R1Record Output unit . . . . . . . . . . . . Printer All results . . . . . . . . . . . . Yes

• Sn(II) is oxidized to Sn(IV) by iodine, and iodine is reduced to iodide.

• Hydrochloric acid must be present in order to supply chloride ions for the oxidation, otherwise the readily hydrolysed Sn(SO4)2 is produced. If necessary, add 5 mL concentrated HCl.

Application note

• Potassium iodate can be used instead of iodine to titrate the sample:

IO3- + 2Sn2+ + 6H+ + Cl- = ICl + 2Sn4+ + 3H2O

KIO3 is standardized with sodium thiosulphate

Na2S2O3 (see application M526).

METTLER TOLEDO


M198 Photometric titration of zinc in a spin bath

Sample: Spin-bath, 5 mL

Substance: Zn2+ , M = 161.4, z = 1 ZnSO4 , M = 65.37, z = 1

Preparation: 10 mL deionized water 50 mL buffer pH 4.5 30 mg Xylenol orange Titrant: EDTA, c(EDTA) = 0.1 mol/L

Standard: Zinc sulphate, ZnSO4 (see appl. M528)



Method: 40008


Indication: DP550 Phototrode with DIN-Lemo adapter ME-89600 30 mg Xylenol orange.

Results:

Results n Comments

Mean value ZnSO4: 5 DL40 application no. 84-22 7.9824 g/L SO4

2- : 4.7875 g/L Rel. standard 0.39 %deviation srel


Authors: Application Laboratoy MT-ANA

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





Sample preparation

1) 5 mL spin bath are diluted in a titration beaker by adding 10 mL deionized water.

2) 50 mL buffer solution pH 4.5 are added3) 30 mg Xylenol orange are added to the sample

solution.

Reaction

• Zinc ions form a red complex with xylenol orange in acidic solution:

Zn2+ + Xylenol 2- → Zn-Xylenol

By adding EDTA during titration, Zn forms a more stable complex with EDTA:

Zn-Xylenol + EDTA 4- → Zn-EDTA + Xylenol 2-

At the equivalence point, all Zn ions have been complexed by EDTA and xylenol orange is free in the acidic solution. There is a colour change from red to yellow.

Chemicals

• Buffer solution pH 4.5: 60 mL glacial acetic acid and 50 g sodium acetat-

eare dissolved in a 1 L volumetric flask. Dilute to the mark with deionized water.

Literature

• DL40 application note no. 84-22• Applications no. M528 in Application bro-

chure18, "Standardization of Titrants", 2000.

MethodMethod 40008 ZnSO4 in spin-bath Version 24-01-2001 11:15

Title Method ID . . . . . . . . . . . . . 40008 Title . . . . . . . . . . . . . ZnSO

4 in spin-bath

Date/time . . . . . . . . . . . . . 24-01-2001 11:15Sample Sample ID . . . . . . . . . . . . . Spin bath Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 5.0 Molar mass M . . . . . . . . . . . . 161.4 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 15 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . EDTA Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . . 2.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 30.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . ZnSO

4 Bath cont.

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q*C2/m Constant . . . . . . . . . . . . . . C2=96.01/z Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . SO

42- in sample

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M199 Determination of sulphate in a spin bath by precipitation titration

Sample: Diluted spin-bath, (1:100) Aliquot 1 mL

Substance: SO42- , M = 96.01, z = 1

Preparation: 20 mL deionized water 30 mL acetone 1 mL mixed indicator Titrant: Barium perchlorate, Ba(ClO4)2 c(Ba(ClO4)2) = 0.005 mol/L

Standard: EDTA (see appl. M540)



Method: 40009


Indication: DP550 Phototrode with DIN-Lemo adapter ME-89600 1 mL mixed indicator.

Results:

Results n Comments

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

332.78 g/L Rel. standard 0.20 %deviation srel

Mean value SO42- : 7 DL40 application no. 106

2.9766 g/L The brine contained 300 g/L i.e. more than 100 times the molar sulphate concentrationRel. 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


Authors: Application laboratoy MT-ANA

DisposalSpecial waste).





Sample preparation

1) 1 mL spin bath are diluted in a 100 mL volumetric flask by adding deionized water.

2) 1 mL aliquot is taken and added to the titration beaker.

3) 20 mL deionized water are added.4) Add 30 mL acetone. Steps 3+4: The aqueous mixture is prepared in ad-

vance and degassed in an ultrasonic bath before use. 50 mL are then added to the sample.

5) If necessary, acidify the sample to pH 3-6 with aqueous perchloric acid 0.05 mol/L.

6) 1 mL mixed indicator is added to the sample prior titration.

Reaction

• Sulphate SO42- is determined by precipitation titra-

tion with barium perchlorate:

SO42- + Ba2+ → BaSO4

• For a better recognition of the endpoint an indicator is added to the sample solution.

Chemicals

• Mixed indicator: In a 50 mL volumetric flask 0.12 mL 1.6% methy-

lene blue solution and 50 mg Thorin are dissolved in 5 mL 0.1 mol/L hydrochloric acid. Fill up to the mark with deionized water.

Literature

• DL40 application note no. 84-22• DL40 application no. 106• Applications no. M528 in Application bro-

chure18, "Standardization of Titrants", 2000.

MethodMethod 40009 SO4

2- in spin-bath Version 24-01-2001 16:30

Title Method ID . . . . . . . . . . . . . 40009 Title . . . . . . . . . . . . . SO

42- in spin-bath

Date/time . . . . . . . . . . . . . 24-01-2001 16:30Sample Sample ID . . . . . . . . . . . . . Spin bath Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 1.0 Molar mass M . . . . . . . . . . . . 96.01 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . Ba(ClO

4)2

Concentration [mol/L] . . . . . . 0.005 Sensor . . . . . . . . . . . . . DP550 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . Yes Volume [mL] . . . . . . . . . . . 3.0 Wait [s] . . . . . . . . . . . . 20 Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 2.0 ∆t [s] . . . . . . . . . . . . . 10.0 t(min) [s] . . . . . . . . . . . 10.0 t(max) [s] . . . . . . . . . . . 45.0 Recognition Threshold . . . . . . . . . . . . 100 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Negative Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . SO

42- sample

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q*100 Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . g/L Result name . . . . . . . . . . . . SO

42- bath

Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M200 Titration of fluoride in soldering salts

Sample: Soldering salts, 1 g

Substance: F - , M = 18.998, z = 1

Preparation: 150 mL deionized water heat at 50°C, 10 minutes 10 mL buffer pH 6 Titrant: Lanthanum nitrate, La(NO3)3 c(1/3 La(NO3)3 ) = 0.1 mol/L

Standard: Sodium fluoride, NaF



Method: 40010

Accessories: 250 mL titration beakers ME-23829

Indication: DX219 Fluoride ISE DX200 Reference electrode (Bridge electrolyte: 1 mol/L KNO3)

Results:

Results n Comments

Mean value F- : 4 DL40 application note 2.17 % no. 8317 Rel. standard 0.20 %deviation srel


Authors: Application Laboratory MT-ANA





Sample preparation

1) Approx. 1 g soldering salts are dissolved in 150 mL deionized water .

2) The sample solution is heated at 50°C under stir-ring during 10 minutes.

3) After cooling to room temperature, 10 mL buffer pH 6 are added before titration.

Reaction

• Fluoride is precipitated by lanthanum in a slightly acid solution:

3 F- + La3+ = LaF3

• 1 mol of La3+ ions reacts with 3 mol of fluoride ions

Chemicals

• Buffer pH 6 solution: Dissolve approx. 85 g sodium acetate in 1 L deion-

ized water. While monitoring the pH value, slowly add glacial acetic acid to achieve pH 6.

• Titrant solution : Dissolve 14.44 g La(NO3)3 • 6H2O in a 1 L volu-

metric flask and fill up to the mark to obtain the concentration c( 1/3 La(NO3)3 ) = 0.1 mol/L.

Literature

• DL40 application note no. 8317

MethodMethod 40010 F- soldering salts Version 24-01-2001 16:30

Title Method ID . . . . . . . . . . . . . 40010 Title . . . . . . . . . . . . . F- soldering salts Date/time . . . . . . . . . . . . . 24-01-2001 16:30Sample Sample ID . . . . . . . . . . . . . Soldering salts Entry type . . . . . . . . . . . . . Weight Lower limit [g] . . . . . . . . . 0.8 Upper limit [g] . . . . . . . . . 1.2 Molar mass M . . . . . . . . . . . . 18.998 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/3 La(NO

3)3

Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DX219 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . No Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.2 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 1.0 ∆t [s] . . . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 45.0 Recognition Threshold . . . . . . . . . . . . 200 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=Q*C/m Constant . . . . . . . . . . . . . . C=M/(10*z) Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . % Result name . . . . . . . . . . . . % F- Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R2=Q*C2 Constant . . . . . . . . . . . . . . C2=M*1000/z Decimal places . . . . . . . . . . . 2 Result unit . . . . . . . . . . . . mg Result name . . . . . . . . . . . . F- sample Statistics . . . . . . . . . . . . . YesCalculation Formula . . . . . . . . . . . . . . R3=VEQ Constant . . . . . . . . . . . . . . Decimal places . . . . . . . . . . . 4 Result unit . . . . . . . . . . . . mL Result name . . . . . . . . . . . . Consumption Statistics . . . . . . . . . . . . . NoReport 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

METTLER TOLEDO


M201 Standardization of 1/2 Pb(NO3)2

Sample: NaF 0.1 mol/L standard solution, 5 mL

Substance: F - , M = 18.998, z = 1

Preparation: 20 mL deionized water 20 mL ispropanol 10 mL buffer pH 6 Titrant: Lead nitrate, Pb(NO3)2 c( 1/2 Pb(NO3)2 ) = 0.1 mol/L

Standard: --



Method: 40011

Accessories: Titration beaker ME-101974

Indication: DX219 Fluoride ISE DX200 Reference electrode (Bridge electrolyte: 1 mol/L KNO3)

Results:

Results n Comments

Mean value Titer : 6 DL40 application no. 102 0.97892 Rel. standard 0.22 %deviation srel


Authors: Application Laboratory MT-ANA





Sample preparation

1) The standard solution is prepared by dissolving 4.200 g NaF in a 1 L volumetric flask and filling up to 1 L with deionized water.

The fluoride solution is kept in polyethylene bot-tles.

2) 5 mL of the standard solution are diluted with 20 mL deionized water, 20 mL isopropanol and 5 mL 0.5 mol/L NaCl.

Reaction

• Fluoride is precipitated by lead according to:

2 F- + Pb2+ = PbF2

• This method can be used for the titration of sulphate ions.

Chemicals

• Titrant solution : Dissolve 16.56 g Pb(NO3)2 in a 1 L volumetric

flask and fill up to the mark to obtain the concentra-tion c( 1/2 Pb(NO3)2 ) = 0.1 mol/L

Literature

• DL40 application no. 102.• C.E. Efstathion, T.P. Hadjhoannon, Anal. Chim. Acta 109 (1979), p. 319.

MethodMethod 40011 Titer Pb(NO3)2 Version 26-01-2001 10:12

Title Method ID . . . . . . . . . . . . . 40011 Title . . . . . . . . . . . . . Titer Pb(NO

3)2

Date/time . . . . . . . . . . . . . 24-01-2001 16:30Sample Sample ID . . . . . . . . . . . . . NaF 0.1 M Entry type . . . . . . . . . . . . . Fixed volume Volume [mL] . . . . . . . . . . . 5 Molar mass M . . . . . . . . . . . . 18.998 Equivalent number z . . . . . . . . 1 Titration stand . . . . . . . . . . Stand 1 Temperature sensor . . . . . . . . . ManualStir Speed [%] . . . . . . . . . . . . . 50 Time [s] . . . . . . . . . . . . . . 30 EQP titration Titrant/Sensor Titrant . . . . . . . . . . . . . 1/2Pb(NO

3)2

Concentration [mol/L] . . . . . . 0.1 Sensor . . . . . . . . . . . . . DX219 Unit of meas. . . . . . . . . . . mV Predispensing . . . . . . . . . . . Yes Volume [mL] . . . . . . . . . . . 4.5 Wait [s] . . . . . . . . . . . . 30 Titrant addition . . . . . . . . . . Incremental ∆V [mL] . . . . . . . . . . . . . 0.1 Measure mode . . . . . . . . . . . . Equilibrium controlled ∆E [mV] . . . . . . . . . . . . . 0.5 ∆t [s] . . . . . . . . . . . . . 3.0 t(min) [s] . . . . . . . . . . . 5.0 t(max) [s] . . . . . . . . . . . 45.0 Recognition Threshold . . . . . . . . . . . . 300 Steepest jump only . . . . . . . No Range . . . . . . . . . . . . . . No Tendency . . . . . . . . . . . . Positive Termination at maximum volume [mL] . . . . . 20.0 at potential . . . . . . . . . . No at slope . . . . . . . . . . . . No after number EQPs . . . . . . . . Yes n = . . . . . . . . . . . . . 1 comb. termination criteria . . . No Evaluation Procedure . . . . . . . . . . . . Standard Potential 1 . . . . . . . . . . . No Potential 2 . . . . . . . . . . . No Stop for reevaluation . . . . . . Yes Condition . . . . . . . . . . neq=0Calculation Formula . . . . . . . . . . . . . . R=m/(VEQ*c*C) Constant . . . . . . . . . . . . . . C=1/(0.1*z) Decimal places . . . . . . . . . . . 5 Result unit . . . . . . . . . . . . Result name . . . . . . . . . . . . Titer Statistics . . . . . . . . . . . . . YesTiter Titrant . . . . . . . . . . . . . . 1/2Pb(NO

3)2

Concentration . . . . . . . . . . . 0.1 Formula t . . . . . . . . . . . . x 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


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.netCheck 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 AGAnalyticalCH-8603 Schwerzenbach, SchweizTelefon (01) 806 77 11, Fax (01) 806 73 50Internet: http://www.mt.com

Subject to technical changes© 04/2007 Mettler-Toledo AG, ME-xxxxxxxxPrinted in Switzerland on 100% chlorine-free pa-per, for the sake of our environment.

For all other countries:Mettler-Toledo GmbHPO Box, VI-400, CH-8606 Greifensee, SchweizTel. (01) 944 22 11, Fax (01) 944 31 70

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

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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

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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

Documents

Electronics and electroplating applications - Mettler · PDF fileM193 Complexometric titration of lead in alloy ... Electronics and electroplating applications METTLER TOLEDO DL5x