AGC Book 20% Cyan Metals Mining

Application Brochure

42

General Titrators

Selected Applications Titration of Metals in the Mining Industry

EDITORIAL

Dear Reader Thank you for reading these lines and looking in our Application Brochure. You can expect detailed descriptions of selected metal determinations via titrimetric analysis. We don't present you a glossy brochure. It is a cookbook with proven recipes.Yet the result is not a cake but a reliable, precise and accurate number. Please follow the recipes diligently to get the most out of your analysis efforts. Titrators of METTLER TOLEDO support you. Easy to use thanks to One Click™ operation and color touchscreen. Simple to set instruments parameters thanks to preprogrammed methods. Smooth to link with your lab data system thanks to LabX software. “The proof of the pudding lies in the eating”, goes a British saying. Thus, we wish you successful "cooking and eating" with our recipes. We are sure that you achieve the top quality results you are working for.

Hans-Joachim Muhr Market Support Manager BA Titration

Georg Reutemann Manager New Projects and Business Development LAB Division

METTLER TOLEDO

Contents
Method Title
Gold - Au M180 M207 M297 M298 M299 Estimation of the Approximate Gold Content in Alloys Titration of Gold -Au(I)- in a Standard Cyanide Solution Standardization of Cerium Sulfate vs. Hydroquinone Standardization of Hydroquinone and Cerium Sulfate with Pure Gold Determination of Gold

Silver - Ag M195 Determination of Silver in Silver Alloys

Cyanide – CNM196 M465 Determination of Free Cyanide in a Cyanidic Silver Bath Determination of Free Cyanide and Silver

Palladium – Pd M462 Determination of Palladium Content

Copper – Cu M460 Iron – Fe M459 M622 M060 Automated Determinaton of Iron Content in Iron Ores Determination of Total Iron Content of Iron Ores Determination of Iron (Fe(II) ) and Sulphuric Acid (H2SO4) Copper Content in Copper Mining Solutions

Chromium – Cr M463 M464 Determination of Cr(III) by Back-Titration in an Electroplating Bath Iodometric Titration of Cr(VI) in an Electroplating bath

Manganese – Mn M461 Determination of Manganese in Manganese Ores

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Metals and metal mining

METTLER TOLEDO
Method Title
Aluminum - Al M466 Boron - B M222 Determination of Boric Acid in Acidic HCl/HF Solutions Aluminum Content in Aluminum Ore (Bauxite) – Bayer Liquor

Titanium -Ti M467 Titanium Content in Mining Solutions

Cobalt - Co M458 Determination of Cobalt Content in Alloy

Uranium - U M292 Determination of Uranium according to Modified Davies-Gray Method

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Metals and metal mining

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Introduction
Metals with all their different material properties have contributed fundamentally to the progress of mankind. Since metals have been available centuries and millenniums ago, a continuous flow of innovations and new developments emerged. Weaponry and ornaments were first produced from metals such as copper, bronze or iron and ended the Neolithic stone age some 5000 years ago. Metals are gained after a long and energy consuming production process from ores. At the end, there is the pure metal which consecutively undergoes further modifications according to its final use. The complete mining process from metallic ores to pure metal can be described as follows:

Geologic survey

Assay of ores

Digging, mining

Size reduction

Concentration

Extraction

Reduction

Refining

Finishing

From the chemical point of view, the reduction reaction of the metal cations of the ores to the elemental metal is in the center of the mining process. Before this step, suitable preparation of the ores such as concentration or extraction is required to separate the metal compound from the rocks. At the beginning, the geologic survey localizes the mineral deposits and assays of the ores evaluate yield expectations and extraction costs. At the end, melting in a blast or electric arc furnace in the presence of a suitable reducing agent such as carbon turns the metal cations from the minerals into the elemental metal. Subsequent refining by electrolytic techniques or other processes produces the pure final metals. The determination of the metal content is thus required at different stages but is always related to the economics of the metals mining process. During the survey, the metal content is a decision factor if the ore is worth mining. Later purposes of analysis are process efficiency and safety or quality and purity of the final products. Noble metals such as gold or silver being nearly resistant to corrosion occur thus as the metal already. The important production process besides the mining is the extraction of the noble metal from its gangue, a process which also requires careful monitoring and control. Titration (titrimetric analysis) is a quantitative analytical method which accompanies the entire chain of the metal mining. It is a well proven and widespread analysis which nowadays comes with a large extent of automation from sample preparation to addition of reagents, result calculation and data storage. METTLER TOLEDO's Excellence line titrators offer the right solution of titrator units, accessories such as sample changers or burettes and software to successfully compete with almost any requirements of titrimetric analysis. The easy One Click™ operation, robust and qualified instruments as well as moderate costs of purchase allow the use of titrators at all mining sites and in small testing labs equally.

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Metals and metal mining

METTLER TOLEDO
The main advantages of titrimetric methods such as linearity and high precision unfurl well appreciated benefits for the user: • Linearity: Unlike spectroscopic techniques, titration is linear over the whole measuring range. Even at high concentrations, no dilution is required. High precision: Typical precision of titrimetric analyses is around 0.5%. In case of pure silver, the relative standard deviation can be as precise as 0.05%.

Equally important are the many titration methods available for the different metals which are tested and approved by a long history of practice. The metals can be divided into different groups either depending on their properties, their occurrence, their use or other criteria. Commonly, base metals, iron and noble metals are distinguished.

Metals Base Metals
Examples:

Ferrous Metals
Example:

Noble Metals
Examples:

• Copper • Aluminium • Nickel • Zinc • Lead • Magnesium • Cobalt

• Iron

• Gold • Silver • Platinum • Rhodium

Ores contain the metals usually as oxides, sulfides or silicates. As an example, the oxides magnetite Fe3O4 and hematite Fe2O3 are the major iron bearing minerals. Chalcopyrite CuFeS2, a sulfide, is the main mineral for the production of copper. Besides the pure metals, alloys and metal compounds play an important role in our current civilization. Structures of skyscrapers and cars are made of metals and alloys to add the requisite strength and mechanical stability. Metals carry the electricity from the point of generation to the point of use hundreds of kilometers (or miles) apart. Or a third example, catalysts from metals or metal compounds support chemical reactions to produce ammonia (from nitrogen and hydrogen) or polymers (from ethylene or propylene), reduce exhaust gases (e.g. in cars) and harden fats and oils (e.g. for use in margarines).

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Metals and metal mining

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Literature
[1] O. Bazhko, “Application of redox titration techniques for analysis of hydrometallurgical solutions”, in: “Hydrometallurgy Conference 2009”, The Southern African Institute of Mining and Metallurgy, 2009. A. I. Samchuk, A. T. Pilipenko, “Analytical Chemistry of Minerals”, Translated from the Russian by S. V. Ponomarenko VNU Science Press, Utrecht, The Netherlands, 1987. K.-H. Spitz, J. Trudinger, “Mining and the Environment: From Ore to Metal”, CRC Press, Taylor & Francis Group, 2009 H. Hartman, J. Mutmansky, “Introductory Mining Engineering”, John Wiley and Sons, 2nd Edition, 2002. B. Lottermoser, “Mine Wastes: Characterization, Treatment and Environmental Impacts”, Springer, Berlin Heidelberg New York, 2nd Edition, 2007.

[2]

[3]

[4]

[5]

Links:
www.slideshare.net/LondonMiningNetwork/ore-mineralogy-and-orebodies Excellent introduction on mining enginering. www.infomine.com InfoMine is a provider of mining knowledge online, delivering content via website, through corporate intranets, and by email. www.greatmining.com Information related to mining and mineral covering all aspects of global mining process from the base exploration to development and from environmental to social issues. www.onemine.org Comprehensive collection of data on mining and minerals based research including technical documents, conference papers, articles, pre-prints and late papers.

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Metals and metal mining

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Metals and metal mining

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Application M180-2010

Estimation of the Approximate Gold Content in Alloys
Estimation of gold content by reduction of gold ions in solution to elemental gold after addition of hydroquinone. Excess hydroquinone is determined by redox titration with cerium sulfate. This method is a fast test of the gold content. Application M299 allows for an accurate determination.

Sample

Various gold alloys with unknown gold content, 30-60 mg Gold, Au M(Au) = 196.967 g/mol, z=3 32% hydrochloric acid, HCl 65% nitric acid, HNO3 0.1 mol/L hydrochloric acid, HCl

Preparation and Procedures
CAUTION: work in a fume hood since gases are produced during dissolution of gold. Alloy dissolution: - Press alloys as thin as possible using a rolling device so that the dissolution is easier. - Use an ultrasonic bath especially for silver containing alloys, because silver chloride does passivate the gold surface. - Weigh 20-30 mg gold sample in a glass beaker. - Add 5 mL HCl 32% and 1.5 mL HNO3 65%, and dissolve it on a heating plate (110-130°C). - Evaporate to almost dryness, but never evaporate to complete dryness. This causes the reduction of gold leading to false results! - Add again 5 mL HCl 32%, and evaporate again to almost dryness, but never evaporate to complete dryness. - Rinse the beaker walls with a small amount (max. 10 mL) of deionized water or 5 mL 32% HCl. Cool down the sample before titration. Titration:

Compound

Chemicals

Titrant

Hydroquinone, C6H6O2 c(1/2 C6H6O2) = 0.05 mol/L Cerium(IV) sulfate, Ce(SO4)2 c(Ce(SO4)2) = 0.01 mol/L

Standard

See M297 and M298 for standardization of titrants DMi140-SC (Pt ring) combined redox electrode
Reduction with hydroquinone:
2Au3+ + 3C6H6O2 → 2Au + 6H+ + 3C6H4O2

Indication

Chemistry

- Place the titration beaker with the prepared sample on the manual titration stand. - 30 mL HCl 0.1 mol/l will be pumped in automatically. - Hydroquinone will be added automatically. The back titration is performed using a DMi140 redox electrode with cerium sulfate 0.01 mol/l.

Titration of excess hydroquinone:
C6H6O2 + 2Ce
4+

→ C6H4O2 + 2Ce

3+

+ 2H

+

Calculation

Content (%): R1 = 100*(H[Hydroquinone]-Q[2])*C/m C1 = M/(1000*z) Content (carat): R2= 24*R1*C2 C2 = M/(1000*z) H[Hydroquinone] (Tx) or H5(DL7x) = dispensed hydroquinone amount

Remarks
1. Pure gold is used as a standard. 2. Theoretical consumption:
20 mg gold corresponds to 7.5 mL hydroquinone, c(1/2 C6H6O2)=0.05 mol/L, and 7.0 mL cerium sulfate, c(Ce(SO4)2)=0.01 mol/L. 1 mL hydroquinone c c(1/2 C6H6O2)=0.05 mol/L corresponds to 5 mL cerium sulfate, c(Ce(SO4)2)= 0.01 mol/L.

Waste disposal

HCl/HNO3: Neutralization with NaOH
Hydroquinone: Evaporate solution,special waste

-

Cerium: Gold:

Precipitate with NaOH, filtrate, special waste Filtrate solution, special waste

Author, Version
METTLER TOLEDO

MSG Anachem, April 1993 Revised January 2010/C. De Caro

Literature: METTLER TOLEDO Application Brochure “Gold and Silver”, ME-724613, 04/1994.
Titration Application M180-2010

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Instruments

- T50/T70/T90 Titration excellence, DL70ES/DL77 Titrators - XS205 Balance
Other titrators: This method can be also run with the DL55 and DL58 titrators (without peristaltic pump).

Accessories

-

2 x 10 mL DV1010 burettes Additional dosing unit (Tx) ME-51109030, or burette drive (DL5x, DL7x) Glass titration beaker ME-101446 SP250 Peristaltic pump ME-5108016

Results
Not available

Titration curve
1st Titration: 2Au3+ + 3C6H6O2 → 2Au + 6H+ + 3C6H4O2

2nd Titration: C6H6O2 + 2Ce4+ → C6H4O2 + 2Ce3+ + 2H+

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Titration Application M180-2010

Table of measured values
Not available

Comments
Principle: To determine pure gold or its content in alloys the precipitation method with hydroquinone has been selected. 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(IV) sulfate: 1. Oxidation of gold: Gold is oxidized to Au3+ by aqua regia (conc. HCl/conc. HNO3 3:1 v/v). 2. Precipitation of gold: Au3+ is reduced by excess hydroquinone and precipitates, and quinone is formed. Au3+ + 3 C6H6O2 = 2 Au + 3 C6H4O2 + 6 H+ 3. Excess hydroquinone is oxidized by cerium(IV) sulfate (back-titration): 2 Ce4+ + C6H6O2 = C6H4O2 + 2 Ce3+ + 2 H+ Estimation of gold content (within approx. 3%): With this method the gold content can be determined within approximately 3%. The gold content can then be determined accurately with application M299. This test method consists of two titration functions: 1st TITRATION function: The gold reduction with hydroquinone is performed by a titration in order • to determine the total amount of C6H6O2 dispensed • to obtain an excess of at least 1 mL C6H6O2 (titrant addition dV = 0.5 mL). The total amount of hydroquinone dispensed is stored as auxiliary value H5. 2nd TITRATION function: Excess hydroquinone is back-titrated back with cerium(IV) sulfate. Maintenance of the electrode: We recommend to always clean the electrode after 6 gold titrations because gold contaminates the platinum ring by forming a thin layer: Place it for two minutes in aqua regia and rinse thoroughly with deionized water (See also leaflet of the DMi140-SC electrode). Literature: - A. Chow, “The Stability of Gold Solutions”, Talanta 18 (1971), pp. 453-456. - S.C. Soundar Rajan and N. Appala Raju, “Titrimetric Determination of Gold by Precipitation with Hydroquinone”, Talanta 22 (1975), pp. 185-189.

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Titration Application M180-2010

DL70ES/DL77 Titrator Method test Version Approximate gold content 10-April-1993 11:09

Titration Excellence Title Type General titration Compatible with T50 / T70 / T90 ID m180 Title Approximate gold content Author admin Date/Time 01.03.2010 10:30:00 Modified at 01.03.2010 10:30:05 Modified by admin Protect No SOP None Sample Number of IDs 1 ID 1 Gold Entry type Weight Lower limit 0.03 g Upper limit 0.06 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 Pump Auxiliary reagent HCl 0.1 mol/L Volume [mL] 40.0 Stir Speed 50% Duration 10 s Condition No Titration (EQP) [1] Titrant Titrant 1/2 C6H6O2 Concentration 0.05 mol/L Sensor Type mV Sensor DMi140-SC Unit mV Temperature acquisition Temperature acquisition No Stir Speed 40% Predispense Mode None Waiting time 0 s Control Control User Titrant addition Incremental dV 0.5 mL Meas. val. acquisition Equilibrium controlled dE 0.5 mV dt 2 s t (min) 10 s t (max) 40 s Evaluation and recognition Procedure Standard Threshold 200 mV/mL Tendency Negative Ranges No Add. EQP criteria No Termination At Vmax 20.0 mL At potential No At slope No After number of recognized EQPs Yes Number of EQP 1 Combined termination criteria No Auxiliary value Name Hydroquinone Formula H= Q[1]+QEX[1] Limits No Stir Speed 50% Duration 120 s Condition No Titration (EQP) [2] Titrant Titrant Ce(SO4)2 Concentration 0.01 mol/L Sensor Type mV Sensor DMi140-SC Unit mV Temperature acquisition Temperature acquisition No

Title Method ID .......................... Title .............................. Date/time .......................... Sample Number samples ..................... Titration stand .................... Entry type ......................... Lower limit [g] ................ Upper limit [g] ................ ID1 ................................ Molar mass M ....................... Equivalent number z ................ Temperature sensor ................. Pump Auxiliary reagent ................. Volume [mL] ........................ Stir Speed [%] .......................... Time [s] ........................... Titration Titrant ............................ Concentration [mol/L] .............. Sensor ............................. Unit of meas. ...................... Titration mode ..................... Titrant addition ............... dV [mL] ...................... Measure mode ................... dE [mV] ...................... dt [s] ....................... t(min) [s] ................... t(max) [s] ................... Threshold ...................... EQP range ...................... Limit A ...................... Limit B ...................... Maximum volume [mL] ............ Termination after n EQPs ....... n = ......................... Evaluation procedure ........... Auxiliary value ID text ........................... Formula ............................ Stir Speed [%] .......................... Time [s] ........................... Titration Titrant ............................ Concentration [mol/L] .............. Sensor ............................. Unit of meas. ...................... Titration mode ..................... Titrant addition ............... dE(set) [mV] ................. Limits dV .................... dV(min) [mL] ............ dV(max) [mL] ............ Measure mode ................... dE [mV] ...................... dt [s] ....................... t(min) [s] ................... t(max) [s] ................... Threshold ...................... EQP range ...................... Limit A ...................... Limit B ...................... Maximum volume [mL] ............ Termination after n EQPs ....... n = ......................... Evaluation procedure ........... Calculation Result name ........................ Formula ........................... Constant ........................... Result unit ........................ Decimal places ..................... Calculation Result name ........................ Formula ........................... Constant ........................... Result unit ........................ Decimal places ..................... Report Output unit ....................... All results ........................

test Approximate gold content 10-April-1997 11:09 1 Stand 1 Weight m 0.03 0.06 Gold 196.967 3 Manual HCl 0.1 mol/L 40.0 50 10 1/2 C6H6O2 0.05 DM140-SC mV EQP INC 0.5 EQU 0.5 2.0 10.0 40.0 200.0 Yes 800 500 20.0 Yes 1 Standard Amount of C6H6O2 H5=Q+QEX 50 120 Ce(SO4)2 0.01 DM140-SC mV EQP DYN 8.0 Absolute 0.02 0.2 EQU 0.5 2.0 3.0 30.0 400.0 Yes 500 700 20.0 Yes 1 Standard content R=100*(H5-Q[2])*C/m C=M/(1000*z) % 1 content R2=24*(H5-Q[2])*C2/m C2=M/(1000*z) carat 1 Printer Yes 003

002

004

005

006

007

008

009

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Titration Application M180-2010

Stir Speed Predispense Mode Waiting time Control Control Titrant addition dE(set value) dV(min) dV(max) Meas. val. acquisition dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQP Combined termination criteria 010 Calculation R1 Result Result unit Formula

40% None 0 s User Dynamic 8.0 mV 0.02 mL 0.2 mL Equilibrium controlled 0.5 mV 2 s 3 s 30 s Standard 400 mV/mL Positive No No 10.0 mL No No Yes 1 No content % R1= 100*(H[Hydroquinone]Q[2])*C/m C=M/(1000*z) M[Gold] z[Gold] 1 No No No No content carat R2= 24*(H[Hydroquinone]-Q[2])*C/m C=M/(1000*z) M[Gold] z[Gold] 1 No No No No No Per Per All No No All All No No No No No No No No No No No No

Constant M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer 011 Calculation R2 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer 012 Record Summary Results Raw results Table of meas. values Sample data Resource data E - V dE/dV - V log dE/dV - V d2E/dV2 - V BETA – V E - t V - t dV/dt - t T – t E – V & dE/dV – V V – t & dV/dt – t Method Series data Condition 013 End of sample

sample sample titration functions

titration functions titration functions

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Titration Application M180-2010

METTLER TOLEDO

Application M207-2010

Titration of Gold -Au(I)- in a Standard Cyanide Solution
Content determination of gold Au(I) in an aqueous solution of potassium dicyanoaurate KAu(CN)2 by precipitation of AgAu(CN)2 with silver nitrate. The titration is monitored with a combined silver ring sensor.

Sample

Standard solution, KAu(CN)2 5 mL c(KAu(CN)2) = approx. 6 g/L Gold, Au M(Au) = 196.967 g/mol, z=1 50 mL deionized water 0.1 mol/L HNO3

Preparation and Procedures
CAUTION: Cyanide is toxic! A too low pH value i.e. below pH 3 leads to the formation of HCN gas which is toxic. Thus, work in a fume hood, use safety googles and wear gloves. Standard solution: - Weigh approx. 1.5 g potassium dicyanoaurate KAu(CN)2 in 250 mL volumetric flask. (This application: 1.46739 g). - Fill up to the mark with deionized water. Titration:

Compound

Chemicals

Titrant

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

- Pipette 5 mL of the above standard solution into a titration beaker. - Add 50 mL deionized water. - Adjust to pH 3-5 by carefully adding 1 mol/L nitric acid (or more concentrated, if necessary).

Standard

Sodium chloride, NaCl See e.g. M525 DMi141-SC (Ag ring) combined metal sensor With Au(I): Ag + Au(CN)2 → AgAu(CN)2 Also possible with Au(III): Ag+ + Au(CN)4- → AgAu(CN)4
+ -

- The titration is performed using a DM141 silver ring electrode with silver nitrate 0.1 mol/l as a titrant.

Indication

Chemistry

Remarks
- The method was developed on a DL40 titrator and was adapted for DL5x, DL7x , G20 and Titration Excellence titrators.

Calculation

Content (g/L): R = Q*C/m C = M/z

Literature: - DL40 application no. 8121, 1981 (customer sample) - METTLER TOLEDO Application Brochure No. 28 “electronics and Electroplating Applications”, 2007 (only available as PDF-file).

Waste disposal

HNO3:

Neutralization with NaOH

Gold, silver: Filtrate solution, special waste

CAUTION: Cyanide is toxic!
MSG Anachem, 1981
Revised February 2010/C. De Caro

- Vogel's textbook of quantitative inorganic analysis, 4th edition, Longman Group Limited, 1978. - See Application M525 (Brochure 18) for the standardization of silver nitrate.

Author, Version
METTLER TOLEDO

Page 1 of 4

Titration Application M207-2010

Instruments

- DL40 MemoTitrator - METTLER TOLEDO Balance, e.g. XS205
Other titrators: This method can be also run with the T50/T70/T90 Titration Excellence and G20 Compact Titrator, and with the DL5x and DL7x instruments (with major changes).

Accessories

- 10 mL DV1010 burettes - Glass titration beaker ME-101446 - Printer

Results
Au+ n Comments

Mean value

3.9978 g/L

5

DL40 application no. 8121

Theoretical Content

4.0134 g/L

1.46739 g KAu(CN)2 in 250 mL deionized water M(KAu(CN)2) = 288.07

Rel. standard deviation srel

0.07 %

Titration curve

METTLER TOLEDO

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Titration Application M207-2010

Table of measured values
Not available

Comments
• Monovalent gold ( Au(I) ), which is present as dicyanoaurate anion in solution, is precipitated as AgAu(CN)2 during titration with silver nitrate: Ag+ + Au(CN)2- → AgAu(CN)2 • A similar precipitation reaction takes place when determining trivalent gold, i.e. Au3+ with silver nitrate as a titrant: Ag+ + Au(CN)4- → AgAu(CN)4 • • Nitric acid 0.1mol/L 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 evaluated. This is due to the precipitation of silver chloride in the sample solution. Gold electroplating baths contain free cyanide ions. Interference from free cyanide ions can be avoided by adjusting the pH to 5-6 using 30-40% formaldehyde solution. Generally, this solution has a pH value between 3 and 4. After a waiting time of 15-20 minutes, the titration can be started. The addition of formaldehyde leads to the formation of cyanohydrin compounds RR’C(OH)CN according to the general reaction between an aldehyde RHC=O or a ketone (RR’C=O) and free cyanide ions: RHC=O + HCN → RHC(OH)CN With formaldehyde, H2C=O, the reaction can be given as: H2C=O + HCN → H2C(OH)CN
METTLER TOLEDO Page 3 of 4 Titration Application M207-2010

Method
T50/T70/T90 Titration Excellence: 001 Title Type General titration Compatible with T50/T70/T90 ID m207 Title Au solution Author Mettler Toledo Date/Time 01.02.2010 15:00:00 Modified at 01.02.2010 15:00:10 Modified by Administrator Protect No SOP None 002 Sample Number of IDs 1 ID 1 KAu(CN)2 Entry type Fixed volume Volume 5.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C 003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Stir Speed 35% Duration 10 s Condition No 005 Titration (EQP) [1] Titrant Titrant AgNO3 Concentration 0.1 mol/L Sensor Type mV Sensor DMi141-SC Unit mV Temperature acquisition Temperature acquisition No Stir Speed 35% Predispense Mode None Waiting time 0 s Control Control User Titrant addition Dynamic dE (set value) 8 mV dV (min) 0.02 mL dV (max) 0.2 mL Mode Equilibrium controlled dE 0.5 mV dt 2 s t (min) 5 s t (max) 30 s Evaluation and recognition Procedure Standard Threshold 800 Tendency Positive Ranges 0 Add. EQP criteria No Termination At Vmax 10 mL At potential No At slope No After number of recognized EQPs Yes Number of EQPs 1 Combined termination criteria No 006 Calculation R1 Result Au Content Result unit g/L Formula R1 = Q*C/m Constant C= M/z M M[Gold] z z[Gold] Decimal places 4 Result limits No Record statistics Yes Extra statistical functions No Send to buffer No Condition No 007 End of sample 008 Report Summary Yes ... DL5x Titrators: Title Method ID ............................m207 Title ................................Au solution Date/time ............................01-02-2010 15:00 Sample Sample ID ............................KAu(CN)2 Entry type ...........................Fixed volume Volume [mL] ..........................5.0 Molar mass M .........................196.97 Equivalent number z .................1 Titration stand ......................Stand 1 Temperature sensor ...................Manual Stir Speed [%] ............................50 Time [s] .............................10 EQP titration Titrant/Sensor Titrant ..............................AgNO3 Concentration [mol/L] ................0.1 Sensor ...............................DM141-SC Unit of meas. .......................mV Predispensing ........................No Titrant addition .....................Dynamic dE(set) [mV] .........................8.0 dV(min) [mL] .........................0.02 dV(max) [mL] .........................0.2 Measure mode ........................Equilibrium .....................................controlled dE [mV] ..............................0.5 dt [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=0 Calculation Formula .............................R=Q*C/m Constant .............................C=M/z Decimal places .......................4 Result unit ..........................g/L Result name ..........................Au content Statistics ...........................Yes Calculation Formula ..............................R2=VEQ Constant ............................. Decimal places .......................3 Result unit ..........................mL Result name ..........................Consumption Statistics ...........................Yes Calculation Formula .............................. Constant ............................. Decimal places .......................0 Result unit .......................... Result name .......................... Statistics ...........................No Report Output ..............................Printer Results ..............................No All results ..........................Yes Raw results ..........................No Table of measured values .............Yes Sample data ..........................No E - V curve ..........................Yes dE/dV - V curve ......................Yes d2E/dV2 - V curve ....................No log dE/dV - V curve ..................No E - t curve ..........................No V - t curve ..........................No dV/dt - t curve ......................No

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Titration Application M207-2010

METTLER TOLEDO

Application M297-2007

Standardization of Cerium Sulfate vs. Hydroquinone
Titer determination of cerium sulfate by redox titration of hydroquinone aqueous solution. The result –a relative factor- is used in applications M298 (standardization hydroquinone and cerium sulfate vs. gold) and M299 (determination of gold).

Sample

Hydroquinone, C6H6O2 c (1/2 C6H6O2) = 0.05 mol/L 1.5 mL Hydroquinone, C6H6O2 M(C6H6O2) = 110.11 g/mol, z=2 0.1 mol/L hydrochloric acid, HCl

Preparation and Procedures
Titration: - Place an empty glass titration beaker on the manual titration stand - 40 mL HCl 0.1 mol/l will be pumped in automatically - 1.5 mL hydroquinone will be dispensed

Compound

Chemicals

- The sample will be titrated with cerium(IV) sulfate 0.01 mol/L using a DMi140-SC sensor. Hydroquinone solution, c(1/2 C6H6O2) = 0.05 mol/L: - Weigh 2.753 g hydroquinone in a glass beaker

Titrant

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

- Transfer with deionized water into a 1 L measuring flask - Add approx. 900 mL deionized water - Add 10 mL H2SO4 96% - Fill up to the mark with deionized water Cerium sulfate solution, c(Ce(SO4)2) = 0.01 mol/L: - Pipette 50.0 mL of cerium sulfate 0.1 mol/L (e.g. Merck 1.09092.1000) in a 500 mL volumetric flask. - Add approx. 400 mL deionized water - Add 10 mL H2SO4 96% and gently mix it - Fill up to the mark with deionized water The cerium(IV) sulfate solution is unstable because a precipitation occurs. It is recommended to prepare a new solution every 2 days. The hydroquinone solution is stable but it is recommended to prepare a new solution every 10 days

Standard

--

Indication

DMi140-SC (Pt ring) combined redox sensor

Chemistry

C6H6O2 + 2 Ce4+ → C6H4O2 + 2 Ce3+ + 2 H+

Calculation

R1 = VENDDi*0.05/(VEQ*c) C1 = 1 Result is stored as auxiliary value: H[Cerium sulfate] = Mean [R1]

Remarks
Theoretical consumption: 1 mL hydroquinone, c(1/2 C6H6O2) = 0.05 mol/L, corresponds to 5 mL cerium(IV) sulfate, c(Ce(SO4)2)= 0.01 mol/L.

Waste disposal

Hydroquinone: Evaporate solution,special waste

Cerium:

Precipitate with NaOH, filtrate, special waste

Author, Version
METTLER TOLEDO

Claudia Schreiner, MSG Anachem, April 2007

Literature: METTLER TOLEDO Application Brochure “Gold and Silver”, ME-724613, 04/1994.

Page 1 of 4

Titration Application M297-2007

Instruments

- T50/70/T90 Titration Excellence with LabX titration - XS205 Balance
Other titrators: This method can be also run with the DL5x and DL7x instruments (with method changes).

Accessories

-

2 x 10 mL DV1010 burettes Additional dosing unit ME-51109030 Glass titration beaker ME-101446 SP250 Peristaltic pump ME-5108016

Results
Start time: Sample No. No. No. No. No. No. Data 1/6 2/6 3/6 4/6 5/6 6/6 22.03.2007 Note / ID Hydroquinone Hydroquinone Hydroquinone Hydroquinone Hydroquinone Hydroquinone Sample size 1.5 mL 1.5 mL 1.5 mL 1.5 mL 1.5 mL 1.5 mL

Results Note / ID Rx Result Unit No. 1/6 Hydroquinone No. 2/6 Hydroquinone No. 3/6 Hydroquinone No. 4/6 Hydroquinone No. 5/6 Hydroquinone No. 6/6 Hydroquinone

R1= R1= R1= R1= R1= R1=

0.9828 0.9822 0.9829 0.9832 0.9833 0.9836

-------

Statistics Rx R1 Name Factor n 6 Mean Value 0.9830 Unit -s 0.0005 srel[%] 0.05

Titration curve

sample 1/5

METTLER TOLEDO

Page 2 of 4

Titration Application M297-2007

Table of measured values
Volume mL
0.000 2.857 4.286 5.000 5.200 5.400 5.600 5.800 6.000 6.200 6.400 6.600 6.800 7.000 7.200 7.400 7.600 7.626 7.631 7.631 7.636 ... 8.270 8.464 8.664 8.664 9.064 9.264 9.464 9.664 9.864 10.000

lncrement mL
NaN 2.857 1.429 0.714 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.026 0.005 NaN 0.005 ... 0.172 0.194 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.136

Signal mV
381.7 429.0 440.1 446.0 448.7 451.4 452.6 454.2 456.0 458.1 460.2 462.9 465.7 469.6 474.2 480.4 502.5 558.2 661.1 664.6 725.9 ... 842.8 850.7 857.6 862.5 867.8 871.4 875.0 878.5 881.2 883.1

Change mV
NaN 47.3 11.1 5.9 2.7 2.7 1.2 1.6 1.8 2.1 2.1 2.7 2.8 3.9 4.6 6.2 22.1 55.7 102.9 NaN 64.8 ... 8.9 7.9 6.9 4.9 5.3 3.6 3.6 3.5 2.7 1.9

1. Derivative mV/mL
NaN NaN NaN NaN NaN 9.01 9.83 9.60 8.75 9.99 11.79 9.55 5.89 21.83 115.11 404.51 1244.86 1962.45 2970.64 NaN 2577.51 ... 49.62 37.38 29.70 25.05 21.28 NaN NaN NaN NaN NaN

Time s
0 14 24 30 39 43 46 50 53 56 59 62 66 70 76 83 86 117 147 NaN 177 ... 301 305 308 313 316 320 323 326 329 332

EQP1 (1)

sample1/5

Comments
To determine pure gold or its content in alloys the precipitation method with hydroquinone has been selected. 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(IV) sulfate: 1. Oxidation of gold: Gold is oxidized to Au3+ by aqua regia (conc. HCl/conc. HNO3 3:1 v/v).

2. Precipitation of gold: Au3+ is reduced by excess hydroquinone and precipitates, and quinone is formed. Au3+ + 3 C6H6O2 = 2 Au + 3 C6H4O2 + 6 H+ 3. Excess hydroquinone is oxidized by cerium(IV) sulfate (back titration): 2 Ce4+ + C6H6O2 = C6H4O2 + 2 Ce3+ + 2 H+ It has been shown (Ref. 1) that copper, iron, zinc, nickel, platinum and palladium do not interfere. We have found in our own work that silver does not interfere. Application M298 (Standardization of hydroquinone and cerium(IV) sulfate vs. gold) and M299 (Determination of gold) complete the whole analysis for the gold content titration. The complete analysis sequence consists of the following steps: 1) M297 2) M298 3) M299

Literature: 1. S.C. Soundar Rajan and N. Appala Raju, “Titrimetric Determination of Gold by Precipitation with Hydroquinone”, Talanta 22 (1975), pp. 185-189. 2. A. Chow, “The Stability of Gold Solutions”, Talanta 18 (1971), pp. 453-456.

METTLER TOLEDO

Page 3 of 4

Titration Application M297-2007

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume Density Correction factor Temperature Entry General titration T50/T70/T90 m297 Factor cerium sulfate Mettler Toledo 05.04.2007 10:39:52 05.04.2007 10:39:52 admin No None Condition Condition 008 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 009 End of sample 010 Auxiliary value Name Formula H= Limits Condition No

Factor R1=VENDDi*0.05/(VEQ*c) 1 M[None] z[None] 5 No Yes No No No

1 Hydroquinone Fixed volume 1.5 mL 1.0 g/mL 1.0 25.0°C Arbitrary

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Pump Auxiliary reagent Volume [mL] Condition 005 Dispense Titrant Concentration Volume Dosing rate Condition 006 Stir Speed Duration Condition 007 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Waiting time Control Control Titrant addition dE (set value) dV (min) dV (max) Mode dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number EPQs Combined termination criteria Accompanying stating Accompanying stating 35% 10 s No HCl 0.1 mol/L 40 No

Cerium sulfate Mean[R1] No No

½ Hydroquinone 0.05 mol/L 1.5 60.0 mL/min No

Cerium sulfate 0.01 mol/L mV DM140-SC mV No 35% Volume 5 5 s User Dynamic 8 mV 0.005 mL 0.2 mL Equilibrium controlled 0.5 mV 2 s 3 s 30 s Standard 500 Positive 0 No 10 mL No No Yes 1 No No

METTLER TOLEDO

Page 4 of 4

Titration Application M297-2007

METTLER TOLEDO

Application M298-2007

Standardization of Hydroquinone and Cerium Sulfate with Pure Gold
Titer determination of hydroquinone by means of pure gold as a standard. Gold ions are reduced to elemental gold after addition of hydroquinone. Excess hydroquinone is determined by redox titration with cerium sulfate. The result is used in M299 (determination of gold).

Sample

Pure gold, 20-30 mg

Preparation and Procedures
CAUTION: work in a fume hood since gases are produced during dissolution of gold.

Compound

Gold, Au M(Au) = 196.967 g/mol, z=3 32% hydrochloric acid, HCl 65% nitric acid, HNO3 0.1 mol/L hydrochloric acid, HCl 96% sulfuric acid, H2SO4 Hydroquinone, C6H6O2 c(1/2 C6H6O2) = 0.05 mol/L Cerium sulfate, Ce(SO4)2 c(Ce(SO4)2) = 0.01 mol/L

Gold dissolution: - Weigh 20-30 mg gold sample in a glass beaker - Add 5 mL HCl 32% and 1.5 mL HNO3 65%. Never use prepared aqua regia, it is unstable! - Dissolve it on a heating plate (110-130°C). - Evaporate to almost dryness, but never evaporate to complete dryness. This causes the reduction of gold leading to false results! - Repeat addition of 5 mL HCl 32%. - Repeat again evaporation to almost dryness, but never evaporate to complete dryness. - Rinse the beaker walls with a small amount (max. 10 mL) of deionized water or 5 mL 32% HCl. Let the sample cool down before starting the titration. Titration:

Chemicals

Titrant

Standard

--

Indication

DMi140-SC (Pt ring) combined redox sensor
Reduction with hydroquinone:
2 Au3+ + 3 C6H6O2 → 2 Au + 6 H+ + 3 C6H4O2

- Place the titration beaker with the prepared sample on the manual titration stand. - 30 mL HCl 0.1 mol/l will be pumped in automatically. - Hydroquinone (1/2 C6H6O2) will be added automatically. Note: The volume to be dispensed is calculated in the method to achieve an optimum titrant consumption of 7 mL. - The back titration is performed using a DMi140SC redox sensor with cerium(IV) sulfate 0.01 mol/l.

Chemistry

Titration of excess hydroquinone:
C6H6O2 + 2 Ce4+ → C6H4O2 + 2 Ce3+ + 2 H+

Calculation

Predispensing Ce(SO4)2 : R1=QENDDi/(H[Cerium sulfate]*0.01)-C C=m*1523*H[Cerium sulfate] Titer hydroquinone vs. gold: R2=C/(QENDDi-VEQ*c*H[Cerium sulfate]) C=(m*1000*z)/M Titer cerium(IV) sulfatevs. gold: R3=Mean[R2]*H[Cerium sulfate] C=1

Remarks
1. Theoretical consumption:
20 mg gold corresponds to 7.5 mL hydroquinone, c(1/2 C6H6O2)=0.05 mol/L, and 7.0 mL cerium sulfate, c(Ce(SO4)2)=0.01 mol/L. 1 mL hydroquinone, c(1/2 C6H6O2)=0.05 mol/L corresponds to 5 mL cerium sulfate, c(Ce(SO4)2)= 0.01 mol/L.

Waste disposal

HCl/HNO3: Neutralization with NaOH
Hydroquinone: Evaporate solution,special waste

-

Cerium: Gold:

Precipitate with NaOH, filtrate, special waste Filtrate solution, special waste

Author, Version
METTLER TOLEDO

Claudia Schreiner, MSG Anachem, April 2007

Literature: METTLER TOLEDO Application Brochure “Gold and Silver”, ME-724613, 04/1994.
Titration Application M298-2007

Page 1 of 7

Instruments

- T70/T90 Titration Excellence with LabX titration - XS205 Balance
Other titrators: This method can be also run with the DL55/DL58 and DL70ES/DL77 titrators with method changes). T50, DL50 Graphix, DL53 and DL67 require manual operations.

Accessories

-

2 x 10 mL DV1010 burettes Additional dosing unit ME-51109030 Glass titration beaker ME-101446 SP250 Peristaltic pump ME-5108016

Results
Start time: Sample Data No. 1/5 No. 2/5 No. 3/5 No. 4/5 No. 5/5 Results No. 1/5 No. 2/5 No. 3/5 No. 4/5 No. 5/5 Statistics Rx R1 R2 27.03.2007 Note / ID Fluka Gold Fluka Gold Fluka Gold Fluka Gold Fluka Gold Note / ID Fluka Gold Fluka Gold Fluka Gold Fluka Gold Fluka Gold Sample size 0.03064 g 0.02525 g 0.02187 g 0.02082 g 0.02255 g Rx R2= R3= R2= R3= R2= R3= R2= R3= R2= R3= Result 1.0004 0.9892 0.9857 0.9747 0.9981 0.9870 1.0036 0.9924 0.9994 0.9872 Unit ----------–

Name Titer 1/2 Hydroquinone vs gold Titer Cerium(IV) sulfatevs gold

n 5 5

Mean Value 0.9974 0.9861

Unit ---

s 0.007 0.007

srel[%] 0.69 0.68

Titration curve

sample 1/5

METTLER TOLEDO

Page 2 of 7

Titration Application M298-2007

Table of measured values
Volume mL 0.000 3.220 4.829 5.634 5.834 6.034 6.234 6.434 6.634 6.834 6.903 6.934 6.950 6.973 6.979 6.934 6.909 6.994 7.007 7.012 7.017 7.017 7.028 7.033 7.041 7.049 7.063 7.092 7.117 7.141 Increment mL NaN 3.220 1.609 0.805 0.200 0.200 0.200 0.200 0.200 0.200 0.069 0.031 0.016 0.023 0.006 0.005 0.005 0.005 0.013 0.005 0.005 NaN 0.011 0.005 0.000 0.000 0.014 0.029 0.025 0.024 Signal mV 479.000 486.800 496.900 503.700 505.600 508.400 511.700 516.100 522.700 536.400 545.500 553.600 558.400 572.500 578.300 585.400 593.700 597.300 623.100 632.700 638.700 639.300 665.600 673.200 684.100 690.500 697.300 708.600 717.000 726.000 1st Derivative mV/mL NaN NaN NaN NaN NaN 24.310 31.110 40.000 63.190 157.890 251.360 370.210 504.270 917.050 1112.690 1107.130 1396.460 1581.450 1905.420 2022.650 1994.060 1953.990 1507.130 1333.730 1134.510 NaN NaN NaN NaN NaN Time s 0.000 10.000 17.000 23.000 38.000 42.000 47.000 52.000 57.000 64.000 67.000 72.000 76.000 86.000 91.000 101.000 114.000 120.000 147.000 160.000 166.000 NaN 192.000 200.000 211.000 210.000 222.000 227.000 232.000 236.000 Temperature °C 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000 NaN 25.000 25.000 25.000 25.000 25.000 25.000 25.000 25.000

EQPI

sample1/5

Comments

Principle: To determine pure gold or its content in alloys the precipitation method with hydroquinone has been selected. 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: 1. Oxidation of gold: Gold is oxidized to Au3+ by aqua regia (conc. HCl/conc. HNO3 3:1 v/v). 2. Precipitation of gold: Au3+ is reduced by excess hydroquinone and precipitates, and quinone is formed. Au3+ + 3 C6H6O2 → 2 Au + 3 C6H4O2 + 6 H+ 3. Excess hydroquinone is oxidized by cerium (IV) sulfate (back titration): 2 Ce4+ + C6H6O2 → C6H4O2 + 2 Ce3+ + 2 H+ It has been shown (Ref. 1) that copper, iron, zinc, nickel, platinum and palladium do not interfere. We have found in our own work that silver does not interfere. Application M297 (Factor cerium(IV) sulfate vs. hydroquinone) and M299 (Determination of gold) complete the whole analysis for the gold content titration. The complete analysis sequence consists of the following steps: 1) M297 2) M298 3) M299

Accuracy: The accuracy which can be obtained by these methods depends on: 1. the weighing and handling procedures e.g. use a balance with high resolution and tweezers 2. the care with which the gold sample is prepared and dissolved. 3. the amount of gold taken. 4. the accuracy of titration method and titrator. Maintenance of the electrode: We recommend to always clean the electrode after 6 gold titrations because gold contaminates the platinum ring by forming a thin layer: Place it for two minutes in aqua regia and rinse thoroughly with deionized water (See also leaflet of the DMi140-SC electrode). Literature: 1. S.C. Soundar Rajan and N. Appala Raju, “Titrimetric Determination of Gold by Precipitation with Hydroquinone”, Talanta 22 (1975), pp. 185-189. 2. A. Chow, “The Stability of Gold Solutions”, Talanta 18 (1971), pp. 453-456.
METTLER TOLEDO Page 3 of 7 Titration Application M298-2007

Principle of titration method

METTLER TOLEDO

Page 4 of 7

Titration Application M298-2007

Principle of titration method

006 Dispense (Hydroquinone) A known excess of hydroquinone is dispensed depending on the size of the gold standard. The optimum titrant consumption for back-titration with cerium(IV) sulfateis set to approx. 7 mL. The predispensing volume VENDDi of hydroquinone solution is calculated accordingly. 008 Calculation (Amount of cerium(IV) sulfateto be predispensed) A predispensing of 70% of cerium(IV) sulfateis used to speed up the titration time. It is calculated based on the predispensing of hydroquinone (QENDDi) and on the gold standard amount. 009 Titration (EQP, back- titration with cerium sulfate) Here the predispensing of cerium(IV) sulfatetitrant is calculated from the result of function 008 Calculation. 010 Calculation (Titer ½ C6H6O2 vs. gold) The titer of hydroquinone, ½ C6H6O2, is determined using pure gold as standard. It is calculated and stored as auxiliary value H[Titer ½ C6H6O2 vs gold] in function 013. 011 Calculation (Titer Ce(SO4)2 vs. gold) The auxiliary value H[Cerium sulfate] is obtained by standardization of cerium(IV) sulfatewith hydroquinone (M297). The titer of cerium sulfate, Ce(SO4)2, must be now referred to pure gold. This is determined in function 011 Calculation. It is stored as auxiliary value H[Titer Ce(SO4)2 vs gold] in function 014. 013 Auxiliary value:
METTLER TOLEDO

H[Titer ½ C6H6O2 vs. gold] = Mean[R2]
Page 5 of 7 Titration Application M298-2007

Principle of titration method
Summary of the method parameters: Parameter Predispense Cerium sulfate Predispense Cerium sulfate Consumption Cerium sulfate Equivalent number of gold Size of gold sample Molar mass of gold Titrant Cerium sulfate Titrant Hydroquinone [g] [g/mol] [mol/L] [mo/L] Symbol VENDDi QENDDi Q z m M c (Ce(SO4)2) c (½ C6H6O2) Unit [mL] [mmol] [mmol] 3 0.02-0.03 196.967 0.01 0.05

Preparation of the reagents
Hydroquinone solution, c(1/2 C6H6O2) = 0.05 mol/L: Note: • • • The cerium(IV) sulfatesolution is unstable because a precipitation occurs. We recommend preparing a new solution every 2 days. The hydroquinone solution is stable but we recommend preparing a new solution every 10 days. Gold sample: Solid gold is dissolved in strong oxidizing acid solution and evaporated to almost dryness (never to complete dryness). If necessary, this procedure has to be repeated until no yellow fumes (nitrous gases) are formed anymore. For the sample sizes used (20-30 mg), the procedure was repeated once. Weigh 2.753 g Hydroquinone in a glass beaker Transfer with deionized water into a 1 L measuring flask Add approx. 900 mL deionized water Add 10 mL H2SO4 96% Fill up to the mark with deionized water Pipette 50.0 mL of cerium(IV) sulfate0.1 mol/L (e.g. Merck 1.09092.1000) in a 500 mL volumetric flask Add approx. 400 mL deionized water Add 10 mL H2SO4 96% and gently mix it Fill up to the mark with deionized water

Cerium(IV) sulfatesolution, c(Ce(SO4)2) = 0.01 mol/L:

METTLER TOLEDO

Page 6 of 7

Titration Application M298-2007

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Lower limit Upper limit Density Correction factor Temperature Entry General titration T50/T70/T90 m298 Factor Hydroquinone Solution Mettler Toledo 08.03.2007 15:01:02 05.04.2007 10:42:46 admin No None dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Combined termination criteria Accompanying stating Accompanying stating Condition Condition 010 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 011 Calculation R3 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 012 End of sample 013 Auxiliary value Name Formula H= Limits Condition 014 Auxiliary value Name Formula H= Limits Condition 0.5 mV 2 s 3 s 30 s Standard 200 Positive 0 No 15 mL No No Yes No No No

1 Gold Weight 0.02 g 0.03 g 1.0 g/mL 1.0 25.0°C Arbitrary

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Pump Auxiliary reagent Volume [mL] Condition 005 Stir Speed Duration Condition 006 Dispense Titrant Concentration Volume Dosing rate Condition 007 Stir Speed Duration Condition 008 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 009 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Waiting time Control Control Titrant addition dE (set value) dV (min) dV (max) Mode 50% 180 s No 50% 5 s No HCl 0.1 mol/L 30 No

Titer ½ C6H6O2 vs. gold R2=
C/(QENDDi-VEQ*c*H[Cerium sulfate])

(m*z*1000)/M M[Gold] z[Gold] 5 No Yes No No No

½ C6H6O2 0.05 mol/L 304.6*m+1.4*H[Cerium sulfate] 60.0 mL/min No

Titer Ce(SO4)2 vs. gold R3=Mean[R2]*H[Cerium sulfate] 1 M[None] z[None] 5 No Yes No No No

Predispense cerium sulfate mL R1=
QENDDi/(H[Cerium sulfate]*0.01)-C

m*1523*H[Cerium sulfate] M[None] z[None] 3 No Yes No No No

Titer 1/2

C6H6O2 vs. gold

Mean[R2] No No

Ce(SO4)2 vs. gold Mean[R3] No No
Titer

Ce(SO4)2 0.01 mol/L mV DM140-SC mV No 40% Volume 0.7*R1 10 s User Dynamic 8 mV 0.005 mL 0.2 mL Equilibrium controlled

METTLER TOLEDO

Page 7 of 7

Titration Application M298-2007

METTLER TOLEDO Determination of Gold

Application M299-2007

Content determination of gold by reduction of gold ions in solution to elemental gold after addition of hydroquinone. Excess hydroquinone is determined by redox titration with cerium(IV) sulfate. Applications M297 and M298 describe the standardization of the used titrants.

Sample

Gold, 20-30 mg

Preparation and Procedures
CAUTION: work in a fume hood since gases are produced during dissolution of gold.

Compound

Gold, Au M(Au) = 196.967 g/mol, z=3 32% hydrochloric acid, HCl 65% nitric acid, HNO3 0.1 mol/L hydrochloric acid, HCl

Gold dissolution: - Weigh 20-30 mg gold sample in a glass beaker - Add 5 mL HCl 32% and 1.5 mL HNO3 65%. - Dissolve it on a heating plate (110-130°C). - Evaporate to almost dryness, but never evaporate to complete dryness. This causes the reduction of gold leading to false results! - Repeat addition of 5 mL HCl 32%.

Chemicals

Titrant

Hydroquinone, C6H6O2 c(1/2 C6H6O2) = 0.05 mol/L Cerium sulfate, Ce(SO4)2 c(Ce(SO4)2) = 0.01 mol/L

- Repeat evaporation to almost dryness, but never evaporate to complete dryness. - Rinse the beaker walls with a small amount (max. 10 mL) of deionized water or 5 mL 32% HCl. Let the sample cool down before starting titration. Titration: - Place the titration beaker with the prepared sample on the manual titration stand. - 30 mL HCl 0.1 mol/l is pumped in automatically. - Hydroquinone (1/2 C6H6O2) will be added automatically. Note: The volume to be dispensed is calculated in the method to achieve an optimum titrant consumption of 6 mL. - The back titration is performed using a DMi140SC redox sensor with cerium(IV) sulfate 0.01 mol/l.

Standard

See M297 and M298 for standardization of titrants DMi140-SC (Pt ring) combined redox electrode
Reduction with hydroquinone:
2Au3+ + 3C6H6O2 → 2Au + 6H+ + 3C6H4O2

Indication

Chemistry

Titration of excess hydroquinone:
C6H6O2 + 2Ce4+ → C6H4O2 + 2Ce3+ + 2H+

Calculation

Content (%): R1= 100*(QENDDi*H[Titer 1/2 C6H6O2 vs gold]Q*H[Titer Ce(SO4)2 vs gold])*C C = M/(m*z*1000) Content (carat): R2= 24*(QENDi*H[Titer ½ C6H6O2 vs gold]-Q*H[Titer Ce(SO4)2 vs gold])*C C = M/(m*z*1000)

Remarks
1. Pure gold is used as a standard. 2. Theoretical consumption:
20 mg gold corresponds to 7.5 mL hydroquinone, c(1/2 C6H6O2)=0.05 mol/L, and 7.0 mL cerium sulfate, c(Ce(SO4)2)=0.01 mol/L. 1 mL hydroquinone c c(1/2 C6H6O2)=0.05 mol/L corresponds to 5 mL cerium sulfate, c(Ce(SO4)2)= 0.01 mol/L.

Waste disposal

HCl/HNO3: Neutralization with NaOH
Hydroquinone: Evaporate solution,special waste

-

Cerium: Gold:

Precipitate with NaOH, filtrate, special waste Filtrate solution, special waste

Author, Version
METTLER TOLEDO

Claudia Schreiner, MSG Anachem, April 2007

Literature: METTLER TOLEDO Application Brochure “Gold and Silver”, ME-724613, 04/1994.
Page 1 of 6 Titration Application M299-2007

Instruments

- T90 Titration Excellence with LabX titration - XS205 Balance
Other titrators: This method can be also run with the T50 and T70 Titration Excellence (if the logical conditions are eliminated), and with the DL5x and DL7x instruments (with major changes).

Accessories

-

2 x 10 mL DV1010 burettes Additional dosing unit ME-51109030 Glass titration beaker ME-101446 SP250 Peristaltic pump ME-5108016

Results
Start time: Sample Data No. 1/3 No. 2/3 No. 3/3 Results No. 1/3 No. 2/3 No. 3/3 Statistics Rx R1 R2 27.03.2007 Note / ID Gold 995 Gold 995 Gold 995 Note / ID Gold 995 Gold 995 Gold 995 Sample size 0.01968 g 0.02061 g 0.02673 g Rx Result R1= 99.958 R2= 23.990 R1= 98.819 R2= 23.717 R1= 99.161 R2= 23.799 n 3 3 Mean Value 99.31 23.84 Correction factor 100 100 100 Unit % Carat % Carat % Carat Unit % Carat s 0.59 0.14 srel[%] 0.6 0.6

Name Purity Carat

Titration curve

sample 1/3

METTLER TOLEDO

Page 2 of 6

Titration Application M299-2007

Table of measured values
Volume mL 0 0.005 0.01 0.022 0.054 0.131 0.325 ... 3.925 4.125 4.325 4.525 4.725 4.925 5.125 5.325 5.525 5.725 5.925 5.998 6.0024 6.003 6.008 6.013 ... 13.915 14.115 14.315 14.515 14.715 14.915 15.0 lncrement mL NaN 0.005 0.005 0.012 0.032 0.077 0.194 ... 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.073 NaN 0.005 0.005 0.005 ... 0.2 0.2 0.2 0.2 0.2 0.2 0.085 Signal mV 471.9 471.7 471.7 471.7 471.7 471.9 472.4 ... 487.2 488.7 490.5 492.2 494.2 496.6 499.4 502.9 507.3 513.8 527.1 596.2 644.4 651 694.4 720.7 ... 887.4 887.8 888.4 889 889.4 890.4 890.4 Change mV NaN -0.2 0 0 0 0.2 0.5 ... 1.2 1.5 1.8 1.7 2 2.4 2.8 3.5 4.4 6.5 13.3 69.1 NaN 54.8 43.4 26.3 ... 0.7 0.4 0.6 0.6 0.4 1 0 1. Derivative mV/mL NaN NaN NaN NaN NaN 1.9 2.68 ... 7.02 7.67 8.48 9.47 10.59 10.94 0.34 11.09 73.22 264.75 797.13 1429.05 NaN 1748.07 1315.63 1739.01 ... 2.85 2.8 NaN NaN NaN NaN NaN Time s 0 3 6 9 12 15 18 ... 73 76 79 82 86 89 92 96 99 102 105 135 NaN 166 196 226 ... 451 454 457 460 463 466 469

sample 1/3

Comments
Principle: To determine pure gold or its content in alloys the precipitation method with hydroquinone has been selected. 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: 1. Oxidation of gold: Gold is oxidized to Au3+ by aqua regia (conc. HCl:conc. HNO3 3:1 v/v). 2. Precipitation of gold: Au3+ is reduced by excess hydroquinone and precipitates, and quinone is formed. Au3+ + 3 C6H6O2 → 2 Au + 3 C6H4O2 + 6 H+ 3. Excess hydroquinone is oxidized by cerium(IV) sulfate (back titration): 2 Ce4+ + C6H6O2 → C6H4O2 + 2 Ce3+ + 2 H+ It has been shown (Ref. 1) that copper, iron, zinc, nickel, platinum and palladium do not interfere. We have found in our own work that silver does not interfere. Application M297 (Factor cerium(IV) sulfate vs. hydroquinone) and M298 (Titer of hydroquinone and cerium(IV) sulfate with pure gold) describe the standardization of the used reagents. The complete analysis sequence involves the following steps: 1) M297 2) M298 3) M299 Accuracy: The accuracy which can be obtained by these methods depends on: 1. the weighing and handling procedures e.g. use a balance with high resolution and tweezers 2. the care with which the gold sample is prepared and dissolved. 3. the amount of gold taken. 4. the accuracy of titration method and titrator. Maintenance of the electrode: We recommend to always clean the electrode after 6 gold titrations because gold contaminates the platinum ring by forming a thin layer: Place it for two minutes in aqua regia and rinse thoroughly with deionized water (See also leaflet of the DMi140-SC sensor). Literature: 1. S.C. Soundar Rajan and N. Appala Raju, “Titrimetric Determination of Gold by Precipitation with Hydroquinone”, Talanta 22 (1975), pp. 185-189. 2. A. Chow, “The Stability of Gold Solutions”, Talanta 18 (1971), pp. 453-456.
METTLER TOLEDO Page 3 of 6 Titration Application M299-2007

Principle of titration method

002 Sample The known gold concentration (in % or in carat) is entered as factor f of the sample in method function 002 SAMPLE. It will be used in the function 004 (or 005) AUXILIARY VALUE. 004 Auxiliary Value / 005 Auxiliary Value In this function the factor of the method function 002 Sample will be used to calculate the H[Fraction Gold] depending on the content of the alloy. 008 Dispense Hydroquinone An excess of hydroquinone is dispensed depending on the amount of gold sample and concentration. Furthermore, the dispensed volume (VENDDi) is calculated for an optimum titrant consumption of 6 mL cerium(IV) sulfate for the back titration.

METTLER TOLEDO

Page 4 of 6

Titration Application M299-2007

Principle of titration method

011 Calculation Purity (percent) The concentration is calculated in percent. 012 Calculation Purity (carat) The concentration is calculated in carat. Parameter Predispense Cerium sulfate Predispense Cerium sulfate Consumption Cerium sulfate Equivalent number of gold Size of gold sample Molar mass of gold [g/mol] Titrant Cerium(IV) sulfate[mol/L] Titrant Hydroquinone [mo/L] Correction factor Symbol VENDDi QENDDi Q z m M c (Ce(SO4)2) c (½ C6H6O2) f Unit [mL] [mmol] [mmol] 3 [g] 196.967 0.01 0.05 % or carat gold of the sample

METTLER TOLEDO

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Titration Application M299-2007

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Lower limit Upper limit Density Correction factor Temperature Entry General titration T90 m299 Gold content Mettler Toledo 21.03.2007 16:02:39 05.04.2007 10:41:10 Administrator No None dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Accompanying stating Condition Condition 011 Calculation R1 Result Result unit Formula 2 s 3 s 30 s Standard 200 Positive 0 No 15 mL No No Yes 1 No No No

1 Gold 995 Weight 0.02 g 0.03 g 1.0 g/mL 24.0 25.0°C Arbitrary

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Auxiliary value Name Formula H= Limits Condition Formula 005 Auxiliary value Name Formula H= Limits Condition Formula 006 Pump Auxiliary reagent Volume [mL] Condition 007 Stir Speed Duration Condition 008 Dispense Titrant Concentration Volume 50% 5 s No HCl 0.1 mol/L 30 No

Purity % R1=
100*(QENDDi*H[Titer 1/2 C6H6O2 vs. gold]-Q*H[Titer Ce(SO4)2 vs. gold])*C

Fraction Gold f/24 No Yes f<=24

Fraction Gold f/100 No Yes f>24ANDf<=100

Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 012 Calculation R2 Result Result unit Formula

M/(m*z*1000) M[Gold] z[Gold] 3 No Yes No No No

Purity in Carat Carat R2=
24*(QENDDi*H[Titer 1/2 C6H6O2 vs gold]-Q*H[Titer Ce(SO4)2 vs. gold])*C

½ C6H6O2 0.05 mol/L
1.2*H[Titer Ce(SO4)2 vs. gold] +304.6*m*H[Fraction Gold]/H[Titer ½ C6H6O2 vs. gold]

Dosing rate Condition 009 Stir Speed Duration Condition 010 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Waiting time Control Control Titrant addition dE (set value) dV (min) dV (max) Mode dE

60.0 mL/min No

Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 013 End of sample

M/(m*z*1000) M[Gold] z[Gold] 3 No Yes No No No

50% 180 s No Note: 1. The method can be easily modified to be run on T50 and T70 Titration Excellence instruments: delete method functions 004 and 005 AUXILIARY VALUE since they contain logical conditions. 2. If the gold content is known (% or carat), then it can be entered as a factor in the method function SAMPLE. In this way, it is possible to calculate the most appropriate predispense for an optimum consumption of 6 mL.

Ce(SO4)2 0.01 mol/L mV DM140-SC mV No 40% None 0 s User Dynamic 8 mV 0.005 mL 0.2 mL Equilibrium controlled 0.5 mV

METTLER TOLEDO

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Titration Application M299-2007

METTLER TOLEDO Determination of Silver in Silver Alloys

Application M195-2010

Content determination of silver Ag(I) in silver alloys by precipitation silver chloride AgCl with sodium chloride as a titrant. The titration is monitored with a combined silver ring electrode. Silver alloys, approx. 0.05 g

Sample

Preparation and Procedures
CAUTION: Work in a fume hood. Concentrated nitric acid is dangerous. Use safety googles, wear gloves and a lab coat.

Compound

Silver, Ag M = 107.868; z = 1

Sample preparation: - Clean the sample with acetone and let it dry – use tweezers.

Chemicals

3 mL 33% nitric acid, HNO3 50 mL deionized water (conc. sulfuric acid)

- Weigh in a sample corresponding to approx. 40 mg Ag and read to ±0.01 mg; then put it in the glass titration beaker. - Add 3 mL of 33% HNO3 and warm up to 60 °C in a water bath until the sample is completely dissolved. - In case of an impure sample add 1 mL of H2SO4 to improve the dissolution. - Let the sample cool down to room temperature. This procedure is a prerequisite to achieve high precision. Titration: - Add 50 mL deionized water. - Start titration. The titration is performed using a DM141-SC silver ring electrode with sodium chloride 0.1 mol/l.

Titrant

Sodium chloride, NaCl, c(NaCl) = 0.1 mol/L

Standard

Silver nitrate, AgNO3 See e.g. M536 DMi141-SC (Ag ring) combined metal electrode Precipitation of silver chloride: Ag+ + Cl- → AgCl

Indication

Chemistry

Remarks
- The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample. - Rinse the electrode after each sample. If necessary, clean the metal ring of the electrode with a paper tissue at the end of each sample series. - High speed: The method was also streamlined to fast titrations. The titration takes less than 2 min.
Literature: - METTLER TOLEDO Application Brochure No. 28 “Electronics and Electroplating Applications”, 2007 (only available as PDF-file).

Calculation

Content (%): R = Q*C/m C = M/(10*z)

Waste disposal

Silver precipitate can be separated (filtration). The filtrated solution is neutralized with NaOH.
Susanne Wahlen, MSG Anachem, May 2010

Author, Version

- Vogel's textbook of quantitative inorganic analysis, 4th edition, Longman Group Limited, 1978.

METTLER TOLEDO

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Titration Application M195-2010

Instruments

- T50/70/90 Titration Excellence - XS205 Balance This method can also be run with the G20 Compact Titrator (with minor adjustments)

Accessories

- 2 x 10 mL DV1010 burette - 1 x additional dosing unit - Glass titration beaker ME-101446 - LabX titration pro

Results
METTLER TOLEDO T90 DL90 Silver Method: MS112B Silver sample Results Series start time 04.06.2010 15:15:25 No. Note / ID Start time Rx Result Unit 1/8 C6: Silver Sample 04.06.2010 15:15:25 R1 = 3.447 mL R2 = 98.077(2)% 2/8 C6: Silver Sample 04.06.2010 15:19:07 R1 = 3.476 mL R2 = 98.912 % 3/8 C6: Silver Sample 04.06.2010 15:22:02 R1 = 3.476 mL R2 = 98.907 % 4/8 C6: Silver Sample 04.06.2010 15:25:29 R1 = 3.477 mL R2 = 98.915 % 5/8 C6: Silver Sample 04.06.2010 15:28:38 R1 = 3.479 mL R2 = 98.972 % 6/8 C6: Silver Sample 04.06.2010 15:31:52 R1 = 3.480 mL R2 = 99.018 % 7/8 C6: Silver Sample 04.06.2010 15:35:37 R1 = 3.479 mL R2 = 98.986 % 8/8 C6: Silver Sample 04.06.2010 15:39:03 R1 = 3.480 mL R2 = 99.024 %

04.06.2010 15:14:54

Name Consumption Silver Content Consumption Silver Content Consumption Silver content Consumption Silver Content Consumption Silver Content Consumption Silver Content Consumption Silver Content Consumption Silver Content

Statistics:
(2) excluded

n = 7

R2 = 98.962 ± 0.051%

s = 0.300

srel: 0.051%

Titration curve

Sample 1/8

METTLER TOLEDO

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Titration Application M195-2010

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

EQP1

0 1.143 1.7145 2 2.4 2.8 3.01 3.1355 3.244 3.3075 3.353 3.4045 3.424 3.439 3.452 3.4655 3.4745 3.47658 3.4835 3.494 3.5045 3.518 3.5365 3.562 3.596 3.6465 3.7185

NaN 1.143 0.5715 0.2855 0.4 0.4 0.21 0.1255 0.1085 0.0635 0.0455 0.0515 0.0195 0.015 0.013 0.0135 0.009 NaN 0.009 0.0105 0.0105 0.0135 0.0185 0.0255 0.034 0.0505 0.072

415.2 403.6 396.3 391.5 382.8 370.3 360.4 352.6 342.3 333.7 326.7 313 305.2 297.4 289.7 279.2 271.2 269.4 263.4 254.2 246.1 237.9 229.4 220.4 212 203 194.6

NaN -11.6 -7.3 -4.8 -8.7 -12.5 -9.9 -7.8 -10.3 -8.6 -7 -13.7 -7.8 -7.8 -7.7 -10.5 -8 NaN -7.8 -9.2 -8.1 -8.2 -8.5 -9 -8.4 -9 -8.4

NaN NaN NaN NaN NaN -50.52 -74.7 -101.94 -143.19 -195.41 -263.64 -396.33 -496.98 -578.52 -655 -740.15 -833.6 -833.98 -816.06 -724.07 -643.32 -570.06 NaN NaN NaN NaN NaN

0 4 7 10 24 27 30 34 37 40 43 46 49 52 55 58 62 NaN 65 68 71 74 77 80 83 86 89

Comments To further improve accuracy and precision, it is recommended to use a microbalance. Furthermore, the sample has to be cleaned using e.g. ethanol, acetone and additional suitable organic solvents to eliminate impurities such as e.g. fatty residues. The sample has to be handled using cleaned tweezers in order to avoid any contact with the fingers (fatty residues). In this application, the sample i.e. the digested silver solution was dispensed with an additional dosing unit in order to achieve a higher repeatability (m = 7 mL).

METTLER TOLEDO

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Titration Application M195-2010

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Weight [g] Density [g/mL] Correction factor Temperature [°C] Entry General titration T50 / T70 / T90 MS112B Silver Sample wahlen 03.06.2010 13:44:05 04.06.2010 15:14:54 wahlen No None Result limits Record statistics Extra statistical func. Send to buffer Condition 009 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 010 Record Summary Results Raw results Table of meas. values Sample data Resource data E - V dE/dV - V log dE/dV - V d2E/dV2 - V BETA – V E - t V - t dV/dt - t T – t E – V & dE/dV – V V – t & dV/dt – t Method Series data Condition 011 End of sample No No No No No

1 Silver wire Fixed weight 0.037837 1.0 1.0 25.0 Arbitrary

Silver Content % R2=Q*C/m M/(10*z) M[Silver] z[Silver] 3 No Yes No No No

003 Titration stand (Manual stand) Type Manual Stand Titration stand Manual Stand 1 004 Stir Speed [%] Duration [s] Condition 005 Dispense (normal)[1] Titrant Concentration Volume [mL] Dosing rate [mL/min] Condition 006 Stir Speed [%] Duration [s] Condition 007 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Volume [mL] Waiting time Control Control Mode Show parameters Titrant addition dE (set value) [mV] dV (min) [mL] dV (max) [mL] Mode dE [mV] dt [s] t (min) [s] t (max) [s] Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax [mL] At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Accompanying stating Condition Condition 008 Calculation R1 Result Result unit Formula Constant C= M z Decimal places 40 10 No 40 1 No

Silver sample 99.9 7.0 60.0 No

No Per sample Per sample Last titration function No No Last titration function Last titration function No No No No No No No No No No No No

NaCl 0.1 mV DM141-SC mV No 30 Volume 2 10 Normal Precipitation Yes Dynamic 9.0 0.008 0.4 Equilibrium controlled 0.5 1.0 3.0 30 Standard 400.0 None 0 No 10.0 No No Yes 1 No No No

Consumption mL R1=VEQ 1 M[None] z[None] 3

METTLER TOLEDO

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Titration Application M195-2010

METTLER TOLEDO

Application M196-2010

Determination of Free Cyanide in a Cyanidic Silver Bath
Free cyanide is precipitated by addition of silver nitrate forming silver dicyanoargentate. The titration is indicated by a silver ring sensor. Silver bath, 1 mL

Sample

Preparation and Procedures
CAUTION: Cyanide is toxic! A too low pH value i.e. below pH 3 leads to the formation of HCN gas which is toxic. Thus, work in a fume hood, use safety googles and wear gloves.

Compound

Potassium cyanide, KCN M = 65.12, z = 1

Sample preparation:

Chemicals

50 mL deionized water,

- 1 mL silver bath is diluted with 50 mL deionized water.

Titration:

Titrant

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

- Start titration. The titration is performed using a DM141-SC silver ring electrode with silver nitrate 0.1 mol/l.

Standard

Sodium chloride, NaCl See e.g. M525

Remarks Indication
DMi141-SC (Ag ring) combined metal sensor Ag+ + 2 CN- → Ag(CN)2First silver excess (precipitate): Ag+ + Ag(CN)2- → Ag[Ag(CN)2] Literature: - The method was developed on a DL67 titrator and has been adapted for T50/T70/T90 Titration Excellence and G20 Compact Titrator.

Chemistry

Calculation

Content (g/L): R = Q*C/m C = M*2 The content is expressed as KCN g/L

- METTLER TOLEDO Application Brochure No. 28 “Electronics and Electroplating Applications”, 2007 (only available as PDF-file). - Application note, DL25 Application Brochure "Petroleum and electroplating", ME-51724627. - Vogel's textbook of quantitative inorganic analysis, 4th edition, Longman Group Limited, 1978. - D.A. Skoog, D.M. West, "Fundamentals of Analytical Chemistry", Holt, Rinehart, and Winston, 1969. - See Application M525 (Brochure 18) for the standardization of silver nitrate.

Waste disposal

Cyanide waste. CAUTION: Cyanide is toxic!

Author, Version
METTLER TOLEDO

Application laboratory, MT-D, 1994 Rev. February 2010 / C. De Caro

Page 1 of 4

Titration Application M196-2010

Instruments

- DL67 Version 3.1 - Balance, e.g. XS205 - Sample changer, e.g. Rondo20
Other titrators: This method can also be run with the T50/T70/T90 Titration Excellence and G20 Compact Titrator (delete “Rinse” function), and with the DL5x and DL7x instruments.

Accessories

-

10 mL DV1010 burettes PP titration beaker ME-101974 SP250 Peristaltic pump ME-51108016 Printer

Results
Method User Measured RESULTS No 1/1 ID1 ID2 Sample amount and results 1.0 R1 = 110.34 R2 = 8.49 1.0 R1 = 111.64 R2 = 8.59 1.0 R1 = 114.09 R2 = 8.78 R1 mL Fixed volume U g/L KCN mL Consumption mL Fixed volume U g/L KCN mL Consumption mL Fixed volume U g/L KCN mL Consumption BL20 KCN im cy.Ag.Bad 24-02-1994 14:49 17-02-1994 10:46

1/2

1/3

STATISTICS Number results Mean value

n = 3 x = 112.02

g/L

KCN

Titration curve

METTLER TOLEDO

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Titration Application M196-2010

Table of measured values
Not available

Comments
• 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 solution remains clear, but the first excess of silver causes formation of a white precipitate silver dicyanoargentate that indicates the endpoint: Ag+ + Ag(CN)2- → Ag[Ag(CN)2]

Since 1 mole of Ag ions reacts with two moles of cyanide ions, the factor 2 is taken into account in the calculation (see constant C).

T50/70/90 Titration Excellence –G20 Compact Titrator No titration method function “Rinse” can be defined when working with the G20 Compact Titrator. Thus, function 006 “Rinse” has to be deleted in order to run the analysis on the G20 titrator.

METTLER TOLEDO

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Titration Application M196-2010

Method
DL7x Titrators: Title Method ID ........................... BL20 Title ............................... KCN im cy.Ag.Bad Date/time ........................... 17-02-1994 10:46 Sample Number samples ...................... Titration stand ..................... Entry type .......................... Volume [mL] ....................... ID1 ................................. Molar mass M ........................ Equivalent number z ................ Temperatur sensor ................... Stir Speed [%] ........................... Time [s] ............................ Titration Titrant ............................. Concentration [mol/L] ............... Sensor .............................. Unit of meas. ...................... Titration mode ...................... Predispensing 1 ................... Volume [mL] .................... Titrant addition .................... dE(set) [mV] ................... Limits dV ...................... dV(min) [mL] ................. dV(max) [mL] ................. Measure mode ....................... dE [mV] ........................ dt [s] ......................... t(min) [s] ..................... t(max) [s] ..................... Threshold ........................... Maximum volume [mL] ................. Termination after n EQPs ............ n = ........................... Evaluation procedure ................ Rinse Auxiliary reagent ................... Volume [mL] ......................... Calculation Result name ......................... Formula ............................ Constant ............................ Result unit ......................... Decimal places ...................... Calculation Result name ......................... Formula ............................ Constant ............................ Result unit ......................... Decimal places ...................... Statistics Ri (i=index) ........................ Standard deviation s ............... Rel. standard deviation srel ........ Outlier test ........................ Record Output unit ......................... All results ......................... 50 10 AgNO3 0.1 DM141-SC mV EQP to volume 1.0 DYN 8.0 Absolute 0.05 0.5 EQU 0.5 1.0 3.0 30.0 50.0 30.0 Yes 1 Standard H2O 10.0 KCN R=Q*C/m C=M*2 g/L 2 Comnsumption R2=VEQ mL 2 R1 Yes Yes Yes Printer Yes 20 ST20 1 Fixed volume 1.0 65.12 1 Manual Titration Excellence: 001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume Density Correction factor Temperature Entry 003 Titration stand (Rondo/Tower Type Titration stand 004 Stir Speed Duration Condition 005 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Waiting time Control Control Titrant addition dE(set value) dV(min) dV(max) Mode dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs 006 Rinse Auxiliary reagent Rinse cycles Vol. Per cycle Position 007 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics . . . 008 End of sample 009 Report Summary . . . General titration T50/T70/T90 m196 KCN im cy.Ag.Bad Mettler Toledo 01.02.2010 08:00:00 01.02.2010 08:00:10 Administrator No None 1 KCN in cyanidic Ag bath Fixed volume 1.0 mL 1.0 g/mL 1.0 25.0°C Arbitrary A) Rondo/Tower A Rondo60/1A 50% 10 s No

AgNO3 0.1 mol/L mV DMi141-SC mV No 35% Volume 1.0 10 s User Dynamic 8.0 mV 0.05 mL 0.5 mL Equilibrium controlled 0.5 mV 1 s 3 s 30 s Standard 50 Positive 0 No 30 mL No No Yes 1 Water 1 10 ml Current position KCN in cyan. Ag-bath g/L R1=Q*C/m M*2 M[KCN] z[KCN] 2 No Yes

Yes

METTLER TOLEDO

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Titration Application M196-2010

METTLER TOLEDO Determination of Free Cyanide and Silver

Application M465-2010

Free cyanide and silver are precipitated as silver dicyanoargentate by addition of silver nitrate; the titration is indicated by a silver ring sensor. Silver cyanidic bath with approx. 8-10 g/L CN- and approx. 20-25 g/L Ag+, 0.5-2 mL Cyanide, CNM = 26.02 g/mol, z = 1 Silver, Ag+ M = 107.868 g/mol, z = 2 50 mL deionized water

Sample

Preparation and Procedures
CAUTION: Cyanide is very toxic! A too low pH value i.e. below pH 3 leads to the formation of HCN gas which is toxic. Thus, work only in a fume hood, use safety goggles, wear gloves and a lab coat. 1) The titer determination of silver nitrate is performed using sodium chloride (NaCl) as a primary standard. Since small amounts of salt cannot be weighed in exactly, it is recommended to prepare an aqueous solution of NaCl, and then to add the standard with a pipette.
+

Compound

Chemicals

Titrant

Silver nitrate, AgNO3 c(½ AgNO3) = 0.2 mol/L
1 mL≙ 2.60 mg CN , 1 mL≙5.39 mg Ag
-

Sodium hydroxide, NaOH, C(NaOH) = 1 mol/L

2) 1-2 mL of silver bath is pipetted in a plastic titration beaker, 50 mL deionized water is automatically added with the diaphragm pump of the Rondo sample changer. 3) The titration is performed using a DMi141-SC silver ring electrode with ½ AgNO3 0.2 mol/l. 4) During titration, the pH is maintained at 12.5 with NaOH using the parameter “Accompanying stating”. Note: The parameters have been optimized for this specific sample. It may be necessary to adapt the method to your sample.

Standard

Sodium chloride, NaCl

Indication

DMi141-SC (Ag ring) DGi112-Pro Ag+ + 2 CN- → Ag(CN)2First silver excess (precipitate): Ag+ + Ag(CN)2- → Ag[Ag(CN)2]

Chemistry

Remarks
Literature:

Calculation

R1 = Q[2]*C/m C = M/z Content expressed as CN- g/L R2 = (QEX[2]+Q[3]-Q[2])*C/m C = M/z Content expressed as Ag+ in g/L

- METTLER TOLEDO Application Brochure No. 28 “Electronics and Electroplating Applications”, 2007 (only available as PDF-file). - Application M196, “Determination of Free Cyanide in a Cyanidic Silver Bath”. - Vogel's textbook of quantitative inorganic analysis, 4th edition, Longman Group Limited, 1978. - D.A. Skoog, D.M. West, "Fundamentals of Analytical Chemistry", Holt, Rinehart, and Winston, 1969. - See Application M525 (Brochure 18) for the standardization of silver nitrate.
Titration Application M465-2010

Waste disposal

Cyanide waste, pH >12 CAUTION: Cyanide is toxic!

Author, Version
METTLER TOLEDO

Claudia Schreiner, MSG Anachem June 2010

Page 1 of 5

Instruments

- T90 Titration Excellence - Balance, e.g. XS205 - Rondo 20 Sample Changer with PowerShower™ and diaphragm pump 2 x 10 mL DV1010 burettes 1 additional dosing Unit PP titration beaker ME-101974 SP250 Peristaltic pump ME-51108016

Accessories

Results
All results Sample R1 R2 Sample R1 R2 Sample R1 R2 Sample R1 R2 Sample R1 R2 Sample R1 R2 Statistics R1 Samples Mean s srel Cyanide 6 9.84 0.09 0.9% content R2 Samples Mean s srel Silver content 6 22.89 0.18 0.80% (Cyanide content) (Silver content) (Cyanide content) (Silver content) (Cyanide content) (Silver content) (Cyanide content) (Silver content) (Cyanide content) (Silver content) (Cyanide content) (Silver content) Cyanide 9.96 22.69 Cyanide 9.89 22.82 Cyanide 9.86 22.80 Cyanide 9.85 22.82 Cyanide 9.73 23.18 Cyanide 9.74 23.05 and Silver Bath (1/6)

and Silver Bath (2/6)

and Silver Bath (3/6)

and Silver Bath (4/6)

and Silver Bath (5/6)

and Silver Bath (6/6)

Titration curve

Cyanide

Silver

METTLER TOLEDO

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Titration Application M465-2010

Table of measured values
Values Cyanide determination Volume mL 0.000 0.050 0.100 0.225 0.425 0.625 0.825 1.025 1.225 1.425 ... 7.806 7.856 7.906 7.956 EQP1 7.985 8.006 8.056 8.106 8.231 8.431 8.631 8.831 9.031 Increment mL NaN 0.05 0.05 0.13 0.20 0.20 0.20 0.20 0.20 0.20 ... 0.05 0.05 0.05 0.05 NaN 0.05 0.05 0.05 0.13 0.20 0.20 0.20 0.20 Signal mV -197.6 -167.1 -168.1 -168.2 -168.2 -168.3 -168.0 -167.6 -167.1 -166.5 ... -79.7 -73.4 -65.3 -53.1 -40.5 -31.5 2.1 5.6 8.1 9.2 9.6 9.9 10.1 Change mV NaN 30.5 -1.0 -0.1 0.0 -0.1 0.3 0.4 0.5 0.6 ... 5.0 6.3 8.1 12.2 NaN 21.6 33.6 3.5 2.5 1.1 0.4 0.3 0.2 1st deriv. mV/mL NaN NaN NaN NaN NaN -2.6 1.8 2.2 2.6 3.0 ... 104.6 184.4 308.6 286.5 325.3 221.5 193.3 177.2 NaN NaN NaN NaN NaN Time s 0 10 20 30 40 50 61 71 81 91 ... 474 484 494 504 NaN 516 539 549 559 570 580 590 600 Temperature °C 25 25 25 25 25 25 25 25 25 25 ... 25 25 25 25 NaN 25 25 25 25 25 25 25 25

Values Silver determination Volume mL 0 0.05 0.1 0.225 0.425 0.625 0.825 ... 7.8555 7.9055 7.9555 EQP1 7.984614 8.0055 8.0555 8.1055 8.2305 8.4305 8.6305 8.8305 9.0305 Increment mL NaN 0.05 0.05 0.125 0.2 0.2 0.2 ... 0.05 0.05 0.05 NaN 0.05 0.05 0.05 0.125 0.2 0.2 0.2 0.2 Signal mV -197.6 -167.1 -168.1 -168.2 -168.2 -168.3 -168 ... -73.4 -65.3 -53.1 -40.5 -31.5 2.1 5.6 8.1 9.2 9.6 9.9 10.1 Change mV NaN 30.5 -1 -0.1 0 -0.1 0.3 ... 6.3 8.1 12.2 NaN 21.6 33.6 3.5 2.5 1.1 0.4 0.3 0.2 1st deriv. mV/mL NaN NaN NaN NaN NaN -2.63 1.77 ... 184.36 308.59 286.5 325.27 221.47 193.33 177.24 NaN NaN NaN NaN NaN Time s 0 10 20 30 40 50 61 ... 484 494 504 NaN 516 539 549 559 570 580 590 600 Temperature °C 25 25 25 25 25 25 25 ... 25 25 25 NaN 25 25 25 25 25 25 25 25

METTLER TOLEDO

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Titration Application M465-2010

Comments
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 solution remains clear, but the first excess of silver causes formation of the white precipitate silver dicyanoargentate that indicates the endpoint: Ag+ + Ag(CN)2- → Ag[Ag(CN)2]

Method The titration of cyanide and silver is a two step procedure. The first step (Titration [2]) determines the cyanide content by using an asymmetric evaluation of the curve. The second step (Titration [3]) determines the silver content using a standard evaluation of the curve.

Method
001 Title Type General titration Compatible with T90 ID CSM196 Title Cyanide and Silver Bath Author Mettler Toledo Date/Time 01.06.2010 14:55:13 Modified at 01.06.2010 16:59:58 Modified by Administrator Protect No SOP None 002 Sample Number of IDs 1 ID 1 Silver bath Entry type Volume Lower limit 0.0 mL Upper limit 5.0 mL Volume 1.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C Entry Arbitrary 003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A 004 Pump Auxiliary reagent WATER Volume 50 mL Condition No 005 Stir Speed 35% Duration 10 s Condition No 006 Measure Sensor Type pH Sensor DG112-Pro Unit pH Temperature acquisition Temperature acquisition No Stir Speed 35% Acquisition of measured values Acquisition Equilibrium dE 0.5 mV dt 1 s t (min) 10 s t (max) 30 Mean value No Condition Condition No

007 Calculation R1 Result pH Result unit Formula R1 = E Constant C= M/z M M[None] z z[None] Decimal places 2 Result limits No Record statistics No Extra statistical funct. No Send to buffer No Condition No 008 Titration (EP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Waiting time Control Control Tendency End point value Control band Dosing rate (max) Dosing rate (max) Termination At EP Termination delay At Vmax Max Time Accompanying stating Accompanying stating Condition Condition Formula

NaOH 1.0 mol/L pH DG112-Pro pH No 35% None 10 s Absolute None 12.5 pH 0.5 pH 10 mL/min 10 mL/min Yes 10 s 20 mL 600s No Yes R1<12.3

METTLER TOLEDO

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Titration Application M465-2010

009 Titration (EQP) [2] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Waiting time Control Control Titrant addition dE(set value) dV(min) dV(max) Mode dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Lower limit Upper limit Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Accompanying stating Titrant Titrant Concentration Continuous addition Sensor Type Name Unit Pretitration Pretitration Predispense Mode Wait time Control Set potential Control band Tendency Dosing rate (max) Dosing rate (min) Monitoring Monitoring Condition Condition 010 Titration (EQP) [3] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Waiting time Control Control Titrant addition dE(set value) dV(min) dV(max)

½ AgNO3 0.2 mol/L mV DM141-SC mV No 35% Volume 0.5 10 s User Dynamic 4.0 mV 0.005 mL 0.1 mL Equilibrium controlled 0.5 mV 2 s 10 s 30 s Asymmetric 200 Positive 1 -400 mV 150 mV No 5 mL No No Yes 1 No Yes NaOH 1.0 mol/L No pH DG112-Pro pH No None 0 s 12.5 pH 0.5 pH Positive 10 mL/min 10 µL/min No No

Mode dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs Accompanying stating Accompanying stating Titrant Titrant Concentration Continuous addition Sensor Type Name Unit Pretitration Pretitration Predispense Mode Wait time Control Set potential Control band Tendency Dosing rate (max) Dosing rate (min) Monitoring Monitoring Condition Condition

Equilibrium controlled 0.5 mV 2 s 10 s 30 s Standard 100 Positive 0 No 10 mL No No Yes 1 Yes NaOH 1.0 mol/L No pH DG112-Pro pH No None 0 s 12.5 pH 0.5 pH Positive 10 mL/min 10 µL/min No No

011 Calculation R2 Result Cyanide content Result unit g/L Formula R2 = Q[2]*C/m Constant C= M/z M M[Cyanide] z z[Cyanide] Decimal places 2 Result limits No Record statistics Yes Extra statistical funct. No Send to buffer No Condition No 012 Calculation R3 Result Silver content Result unit g/L Formula R3 = (QEX[2]+Q[3]-Q[2])*C/m Constant C= M/z M M[Silver] z z[Silver] Decimal places 2 Result limits No Record statistics Yes Extra statistical funct. No Send to buffer No Condition No 013 Rinse Auxiliary reagent Rinse cycles Vol. Per cycle Position Drain Drain pump Condition 014 Conditioning Type Interval Position Time Speed Condition 015 End of sample

½ AgNO3 0.2 mol/L mV DM141-SC mV No 35% None 0 s User Dynamic 4.0 mV 0.05 mL 0.2 mL

WATER 3 20 ml Current sample Yes DRAIN No

Fix 1 Conditioning beaker 30 s 30 % No

METTLER TOLEDO

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Titration Application M465-2010

METTLER TOLEDO Determination of Palladium Content

Application M462-2010

Palladium(II) was determined by potentiometric titration with hexadecylpyridinium chloride (HDPCl) using a surfactant sensitive electrode in combination with a reference electrode. Palladium chloride, PdCl2 c(PdCl2) = 0.01 mol/L

Sample

Preparation and Procedures
Hexadecylpyridinium chloride (HDPCl, 0.02 mol/L): - 7.16020 g HDPCl monohydrate is cautiously dissolved (avoid foam formation) in 200-300 mL deionized water in a 1 L volumetric flask. - The flask is slowly filled up with deionized water. - Note: HDPCl is also called cetylpyridinium chloride (CPC). Sodium dodecylsulfate (SDS, 0.004 mol/L): - 1.15352 g is added into a 1 L volumetric flask, which is slowly filled up with deionized water to avoid the formation of foam. Palladium chloride, PdCl2 (0.01 mol/L): - 0.18230 g is added in a 100 mL volumetric flask. - The flask is filled with approx. 80 mL mixed solution (0.5 mol/L NaCl in 0.5 mol/L HCl). - PdCl2 dissolves slowly while stirring. After complete dissolution, fill up to the mark by adding further mixed solution. Titer determination of HDPCl: - 10 mL SDS (0.004 mol/L) was added to 50 mL deionized water and subsequently titrated with HDPCl.

Compound

Palladium(II), Pd2+ M = 106.42 g/mol, z = 2

Chemicals

-

Mixed solution: 0.5 mol/L NaCl in 0.5 mol/L HCl Ethanol

Titrant

Hexadecylpyridinium chloride HDPCl,

c(HDPCl) = 0.02 mol/L

Standard

Sodium dodecylsulfate (SDS) c(SDS) = 0.004 mol/L - DS800 TwoPhase
surfactant sensitive sensor

Indication

-DX200 Reference half-cell

Chemistry

PdCl2 + 2 C21H38NCl [Pd(II)(C21H38N)2]Cl4

Remarks
Sample preparation: - 5 mL 0.01 mol/L PdCl2 solution is added into a titration beaker. - 50 mL mixed solution (0.5 mol/L NaCl in 0.5 mol/L HCl) is automatically added by an additional dosing unit. - Subsequently, 5 mL ethanol is added to ensure complete dissolution of PdCl2, and also to reduce foaming as well as flocculation during titration. Calculations: For all calculations, the actual concentrations calculated on the basis of the actual sample mass have been used (see preparation and procedures). A recovery of 101.983% for Pd(II) was obtained.

Calculation

R1 = VEQ, [mL] R2 = Q*C/m C = 1/z, [mol/L], z = 2

Waste disposal

Pd(II) as aqueous heavy metal waste

Author, Version
METTLER TOLEDO

Thomas Hitz, MSG Anachem, May 2010

Page 1 of 4

Titration Application M462-2010

Instruments

- T50/T70/T90 Titration Excellence - XS205 Balance - Rondolino sample changer 1 additional dosing unit 2 x 10 mL DV1010 burette Titration beaker ME-101974 LabX pro titration software

Accessories

Results
All results Method-ID Sample R1 (Consumption) Sample R1 (Consumption) Sample R1 (Consumption) Sample R1 (Consumption) Sample R1 (Consumption) Sample R2 (Content) Sample R2 (Content) Sample R2 (Content) Sample R2 (Content) Sample R2 (Content) Statistics Method-ID R2 Samples Mean s srel m462 Content 5 0.01049 mol/L 0.00007 mol/L 0.647% m462 PdCl2 (1/5) 5.25996 mL PdCl2 (2/5) 5.23816 mL PdCl2 (3/5) 5.20766 mL PdCl2 (4/5) 5.19172 mL PdCl2 (5/5) 5.18240 mL PdCl2 (1/5) 0.01058 mol/L PdCl2 (2/5) 0.01054 mol/L PdCl2 (3/5) 0.01047 mol/L PdCl2 (4/5) 0.01044 mol/L PdCl2 (5/5) 0.01042 mol/L

Titration curve

METTLER TOLEDO

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Titration Application M462-2010

Table of measured values
Volume mL 0 2.5 2.55 2.6 2.65 2.7 2.75 2.8 4.9 4.95 5 5.05 5.1 5.15 5.2 5.25 5.259959 5.3 5.35 5.4 5.45 5.5 5.55 5.6 5.65 5.7 5.75 NaN 2.5 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 NaN 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 Increment mL Signal mV 107.1 122.7 120.1 119.9 119.9 119.9 119.8 119.8 127.2 127.8 128.5 129.3 130.2 131.2 132.3 134.2 134.7 136.8 138.2 139.3 140 140.8 141.3 141.7 142.4 142.7 143.1 Change mV NaN 15.6 -2.6 -0.2 0 0 -0.1 0 0.5 0.6 0.7 0.8 0.9 1 1.1 1.9 NaN 2.6 1.4 1.1 0.7 0.8 0.5 0.4 0.7 0.3 0.4 1st deriv. mV/mL NaN NaN NaN NaN NaN -5.14 2.64 -0.28 11.45 12.97 13.95 15.35 20.4 26.92 32.86 35.55 35.56 34.59 29.91 22.24 15.16 11.23 10.66 9.77 8.68 7.76 7.02 Time s 0 13 78 84 89 94 99 104 317 322 327 332 337 342 348 355 NaN 364 369 374 379 384 389 394 400 405 410 Temperature °C 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 25 NaN 25 25 25 25 25 25 25 25 25 25

EQP1

Comments • • In this application, the sample is diluted by automatically adding 50 mL NaCl/HCl solution using an additional dosing unit. This step can be also performed manually prior titration. In this case, the method function “Dispense” has to be deleted.

METTLER TOLEDO

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Titration Application M462-2010

Method
001 Title Type Compatible with Method ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume [mL] Density [g/mL] Correction factor Temperature [°C] General titration T50 / T70 / T90 m462 Pd analysis hitz 10.05.2010 10.05.2010 hitz No None Record statistics Extra statistical func. Send to buffer Condition 008 Calculation R2 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 009 Record Summary Results Raw results Table of meas. values Sample data Resource data E - V dE/dV - V log dE/dV - V d2E/dV2 - V BETA – V E - t V - t dV/dt - t T – t E – V & dE/dV – V V – t & dV/dt – t Method Series data Condition 010 End of sample mV DS800 mV No 30 Volume 2.5 60 User Incremental 0.05 Equilibrium controlled 0.5 2.0 5 30.0 Standard 15 Positive 0 Steepest jump 1 7 No No No No No Yes No No No

1 PdCl2 Fixed volume 5 1.0 1.0 25.0

Content Pd mol/L R2=Q*C/m C=1/z M[Palladium] z[Palladium] 5 No Yes No No No

003 Titration stand (Rondolino TTL) Type Rondolino TTL Titration stand Rondolino TTL 1 004 Dispense (normal) [1] Titrant Concentration [mol/L] Volume [mL] Dosing rate [mL/min] Condition 005 Stir Speed [%] Duration [s] Condition 006 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Volume [mL] Wait time [s] Control Control Titrant addition dV [mL] Mode dE [mV] dt [s] t (min)[s] t (max)[s] Evaluation and recognition Procedure Threshold [mV/mL] Tendency Ranges Add. EQP criteria Steepest jumps Termination At Vmax [mL] At potential At slope After number of recognized EQPs Combined termination criteria Accompanying stating 007 Calculation R1 Result Result unit Formula Constant M z Decimal places Result limits 30 30 No

HCl/NaCl 0.5 50 60.0 No

HDPCl 0.02

No Per Per All No No All All No No No No No No No No No No No No

sample sample titration functions

titration functions titration functions

Consumption HDPCl mL R1=VEQ C=1 M[None] z[None] 5 No

METTLER TOLEDO

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Titration Application M462-2010

METTLER TOLEDO Copper Content in Copper Mining Solutions

Application M460-2010

Determination of copper content in intermediate products in copper mining. Copper is determined by iodometric titration with sodium thiosulphate as a titrant. The redox reaction is indicated by a platinum pin sensor with plastic shaft.

Sample

Leach solution from copper ore, e.g. Chalcopyrite (CuFeS2 ). 5 mL Copper, Cu2+, M = 63.55 g/mol, z=1 KI solution, 10% w/w ammonium hydrogen fluoride solution, (NH4)(HF2) ~0.3 M solution for excess (add > 5 mL)

Preparation and Procedures
CAUTION: Due to the presence of hydrofluoric acid, HF, in the solution, always work in a fume cupboard, wear gloves, safety glasses and a lab coat. • Depending on the expected concentration of Cu2+ in the sample solution, the amount of sample is chosen in such a way that the final amount of Cu2+ in the titration vessel is ~ 0.5 mmol. • To the sample solution, excess ammonium hydrogen fluoride (NH4)(HF2) is added for masking of Fe3+ (see ‘Chemistry’). If any Fe3+ is present freely in the solution it will interfere with the Cu2+ determination by reacting with the thiosulphate to form Fe2+. Enough excess of potassium iodide, KI, is added to ensure that all the Cu2+ ions present in the solution can react to form I2. Subsequently, the generated I2 is then titrated with sodium thiosulphate, Na2S2O3, to determine the copper content via iodometric titration.

Compound

Chemicals

Titrant

Sodium thiosulfate, Na2S2O3 c(Na2S2O3) = 0.1 M •

Standard

Potassium iodate, KIO3

Indication

- DM240-SC - DX202 (reference) 2 Cu2+ + 4 II2 + 2 S2O32Fe3+ + 6 F→ 2 CuI + I2 → 2 I- + S4O62 → [FeF6]3-

Remarks
Because of the presence of HF in the solution, extreme care has to be taken in handling the samples. Neutralize the sample to annihilate the danger from HF Before final disposal. In addition to masking of the Fe3+, (NH4)(HF2) also keeps the pH at a low enough value for the redox reaction to complete fully. Should no (NH4)(HF2) be added, please make sure to add e.g. HCl to keep the pH low enough.

Chemistry

Calculation

Content (g/L) R1 = Q*C/m C = M/z Content (mol/L) R2 = Q*C/m C = 1/z

-

Waste disposal

Neutralised HF solutions do not require special disposal. Copper and iron should be disposed as heavy metals. Melanie Nijman, MSG Anachem, March 2010

Author, Version
METTLER TOLEDO

Note: • The addition of (NH4)(HF2) to the sample cannot be automated with a dosing unit as the fluoride in acidic environment would corrode the glass of the burette. A peristaltic pump can be used, indeed. • Addition of the KI solution can be automated with an extra dosing unit, indeed.

Page 1 of 4

Titration Application M460-2010

Instruments

- T50/T70/T90 Titration Excellence - XS205 Balance - Rondo 20 sample changer - 2 x 10 mL DV1010 burettes - Titration beakers ME-101974 - LabX pro titration software

Accessories

Results
Samples 1/6 2/6 3/6 4/6 5/6 6/6 Results 1/6 2/6 3/6 4/6 5/6 6/6 Copper solution Copper solution Copper solution Copper solution Copper solution Copper solution Comment / ID Copper solution Copper solution Copper solution Copper solution Copper solution Copper solution 5.0 mL 5.0 mL 5.0 mL 5.0 mL 5.0 mL 5.0 mL Rx R1 = R2 = R1 = R2 = R1 = R2 = R1 = R2 = R1 = R2 = R1 = R2 = Statistics Rx R1 R2 Name Content Content n 6 6 Mean value 6.3853 0.10049 Unit g/L mol/L s 0.0081 0.00013 srel [%] 0.128 0.130 Result 6.3795 0.10040 6.3862 0.10051 6.3855 0.10050 6.4007 0.10074 6.3808 0.10042 6.3790 0.10039 Unit g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L Name Content Content Content Content Content Content Content Content Content Content Content Content

Titration curve

METTLER TOLEDO

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Titration Application M460-2010

Table of measured values
Volume mL 0 0.02 0.04 0.09 0.215 0.415 0.615 0.815 1.015 1.215 1.415 1.615 1.815 2.015 2.215 2.415 2.615 2.815 3.015 3.215 3.415 3.615 3.815 4.015 4.215 4.415 4.615 4.815 4.9805 5.025 5.045532 5.0485 5.0845 5.1045 5.1545 5.1925 5.2875 5.4875 5.6875 5.8875 6.0875 Increment mL NaN 0.02 0.02 0.05 0.125 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.2 0.1655 0.0445 NaN 0.0235 0.036 0.02 0.05 0.038 0.095 0.2 0.2 0.2 0.2 Signal mV 355.9 356 355.9 355.8 355.5 354.8 354.2 353.5 352.7 351.9 351.1 350.4 349.4 348.6 347.6 346.4 345.3 344.1 342.7 341.2 339.5 337.6 335.3 332.7 329.8 325.7 320.3 311.5 296.8 289 285 284.4 272.5 268.3 257.6 255.7 255.3 256.7 257.3 256.3 255.1 Change mV NaN 0.1 -0.1 -0.1 -0.3 -0.7 -0.6 -0.7 -0.8 -0.8 -0.8 -0.7 -1 -0.8 -1 -1.2 -1.1 -1.2 -1.4 -1.5 -1.7 -1.9 -2.3 -2.6 -2.9 -4.1 -5.4 -8.8 -14.7 -7.8 NaN -4.6 -11.9 -4.2 -10.7 -1.9 -0.4 1.4 0.6 -1 -1.2 1st deriv. mV/mL NaN NaN NaN NaN NaN -3.16 -3.54 -3.65 -3.83 -3.92 -4.01 -4.17 -4.44 -4.78 -5.17 -5.57 -5.98 -6.51 -7.09 -7.99 -8.94 -10 -11.05 -11.92 -16.13 -25.43 -44.09 -85.99 -154.76 -165.77 -169.75 -139.72 -163.95 -120.18 -125.93 -99.48 NaN NaN NaN NaN NaN Time s 0 14 17 20 23 26 29 32 35 38 41 44 47 50 53 56 59 62 65 69 72 75 79 83 86 90 94 99 104 107 NaN 110 114 118 121 125 128 131 134 137 140

EQP1

Comments
• Because of the presence of hydrofluoric acid in the sample to be titrated, no glass redox electrode can be used (e.g. DMi140-SC). Especially for these kinds of applications, the polymer redox halfcell DM240-SC sensor has been developed, which is used in this application (see picture on the right). This sensor consists of a platinum wire mounted into a plastic shaft. In addition to the DM240-SC half-cell redox sensor, the special polymer reference sensor DX202-SC is used, which is also suitable for use in HF solutions (see e.g. M366).

• •

METTLER TOLEDO

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Titration Application M460-2010

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume [mL] Density [g/mL] Correction factor Temperature [°C] General titration T50 / T70 / T90 MN409 Copper content HF Administrator 18.03.2010 10:20:38 19.03.2010 13:31:07 Administrator No None M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 008 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 009 Rinse Auxiliary reagent Rinse cycles Vol. per cycle[mL] Position Drain Condition 010 Conditioning Type Interval Position Time [s] Speed [%] Condition 011 End of sample Na2S2O3 0.1 mV DM240-SC mV No 30 None 10 User Dynamic 8.0 0.02 0.2 Equilibrium controlled 1.0 2 3 10 Standard 80 None 0 No M[Copper] z[Copper] 4 No Yes No No No

1 Copper Solution Fixed volume 5.0 1.0 1.0 25.0°C

003 Titration stand (Rondo/TowerA) Type Rondo/Tower A Titration stand Rondo60/1A Lid handling No 004 Stir Speed [%] Duration [s] Condition 005 Dispense (normal) [1] Titrant Concentration Volume [mL] Dosing rate [mL/min] Condition 006 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Wait time [s] Control Control Titrant addition dE (set value) [mV] dV (min) [mL] dV (max) [mL] Mode dE [mV] dt [s] t (min) [s] t (max) [s] Evaluation and recognition Procedure Threshold [mV/mL] Tendency Ranges Add. EQP criteria Termination At Vmax [mL] At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Condition 007 Calculation R1 Result Result unit Formula Constant C= 30 10 No

Content mol/L R2=Q*C/m 1/z M[None] z[None] 5 No Yes No No No

Water 1 20 Current position No No

10% KI 1 10 60.0 No

Fix 1 Conditioning beaker 10 30 No

10.0 No No Yes 1 No No No

Content g/L R1=Q*C/m M/z

METTLER TOLEDO

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Titration Application M460-2010

METTLER TOLEDO

Application M459-2010

Automated Determination of Iron Content in Iron Ores
The iron content in iron ores is determined by redox titration in strong acid solution with potassium dichromate K2Cr2O7 as a titrant. The potential change is monitored by a combined platinum ring electrode.

Sample

Iron ores, 0.08 - 0.15 g Approx. 60% iron content Iron, Fe M = 55.85; z = 1

Preparation and Procedures
CAUTION: Work in a fume hood, use safety goggles and wear gloves.

Compound

Sample dissolution: - Approximately 0.05 to 0.1 g of iron powder is accurately weighed into a glass titration beaker. - 40 mL concentrated HCl is added. - The sample is then gently heated (70-90°C) on a hot plate while stirring until complete iron. Let the sample cool down. Titration: - Prior to titration with K2Cr2O7, Fe(III) has to be reduced to Fe(II) by tin chloride, SnCl2, to yield the total iron content. - The addition of SnCl2 can be automated by means of an endpoint titration function. Initially, the potential needs to be determined where the solution turns colorless when adding SnCl2. In this case, the endpoint was set to 120 mV. - Add 3 mL of each concentrated phosphoric and sulfuric acid for better endpoint detection. This optimizes the reduction potential and potential interferences by Fe(III) are suppressed by its complexation with PO43-. - EQP: The titration by K2Cr2O7 shows two equivalence points: The first is caused by the excess ofSnCl2 while the second EQP corresponds to the iron content.

Chemicals

Conc. hydrochloric acid, HCl Conc. sulphuric acid, H2SO4 Conc. phosphoric acid, H3PO4 Deionized water

Titrant

Potassium dichromate, K2Cr2O7 c(1/6 K2Cr2O7) = 0.1 mol/L Tin(II) chloride, SnCl2 c(SnCl2) = 1 mol/L For K2Cr2O7: (NH4)2Fe(SO4)2 Combined redox Pt-sensor e.g. DMi140-SC
Reduction to Fe(II): 2 Fe3+ + Sn2+ → 2 Fe2+ + Sn4+ Titration: 6 Fe2+ + 6 Fe3+ +
2-

Standard Indication

Chemistry

Cr2O7 2 Cr3+

+ 14 H+ + 7 H2O

Remarks
- The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample. - SnCl2 solution (approx. 1 mol/L): 30 g SnCl2 x 2 H2O (M = 225.63) is dissolved 100 mL conc. HCl, and diluted to 200 mL with deionized water. - Rinse the sensor after each sample. If necessary, clean the metal ring of the redox electrode with a paper tissue at the end of a sample series.

Calculation

Content • R1 = Q*C/m • C = M/(10*z)

Waste disposal

Neutralize the sample with sodium hydroxide before final disposal as special waste (Chromium).
Susanne Wahlen, MSG Anachem, April 2010 Revised May 2010 / C. De Caro Craig Gordon, MSG Anachem, May 2005

Author, Version

METTLER TOLEDO

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Titration Application M459-2010

Instruments

- T70/90 Titration Excellence (T50: Dispensing of SnCl2 solution with “Dispense” function) - XS205 Balance - Rondo 20 Sample Changer with PowerShower™ 2 x 10 mL DV1010 burette 2 x 5 mL DV1005 burette 3 x additional Dosing Units (EP/Dispense with SnCl2, dosing of H3PO4 and H2SO4) Glass titration beaker ME-101446 LabX titration pro

Accessories

Results (T70/T90)
METTLER TOLEDO T90 T90 Fumehood Method: Results Series start time No. Comment/ID 1/8 Iron Ore(Greece) 24.03.2010 14:23:33 Start time Rx 24.03.2010 14:23:33 R1 R2 R3 24.03.2010 14:23:33 R1 R2 R3 24.03.2010 14:51:09 R1 R2 R3 24.03.2010 15:04:14 R1 R2 R3 24.03.2010 15:16:22 R1 R2 R3 24.03.2010 15:29:39 R1 R2 R3 24.03.2010 15:42:50 R1 R2 R3 24.03.2010 15:55:44 R1 R2 R3 MS1055 Fe(II) in Ore (Rondo) 24.03.2010 14:22:41

2/8

Iron Ore(Greece)

3/8

Iron Ore(Greece)

4/8

Iron Ore(Greece)

5/8

Iron Ore(Greece)

6/8

Iron Ore(Greece)

7/8

Iron Ore(Greece)

6/8 Iron Ore(Greece)

= = = = = = = = = = = = = = = = = = = = = = = =

Result Unit NaN mL 2.881 mL 37.953(2) % 0.450 mL 6.904 mL 38.692 % 0.446 mL 6.816 mL 38.195 % 0.444 mL 6.982 mL 39.126(2) % 0.447 mL 6.845 mL 38.358 % 0.444 mL 6.819 mL 38.216 % 0.438 mL 6.859 mL 38.436 % 0.440 mL 6.850 mL 38.385 % s = 0.180%

Name EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content EP Consumption 2nd EQP Consumption Iron Content srel = 0.469%

Statistics: (2)

n = 6 Excluded

R3 = 38.380 ± 0.180%

METTLER TOLEDO

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Titration Application M459-2010

Titration curve (T70/T90)

Table of measured values (T70/T90)
Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s --------------------------------------------------------------------------------------------

EQP1

0 0.02 0.04 0.06 0.096 0.141 0.1885 0.2565 0.2855 0.358 0.378 0.428 0.448 0.468 0.5015 0.5215 0.5415 0.5615 0.5815 0.58904 0.6015 0.6215 0.6415 0.6615 0.6815 0.702 0.7355 0.7935 0.878 0.976 1.128 1.3085 1.5425 1.837 2.137 2.437

NaN 0.02 0.02 0.02 0.036 0.045 0.0475 0.068 0.029 0.0725 0.02 0.05 0.02 0.02 0.0335 0.02 0.02 0.02 0.02 NaN 0.02 0.02 0.02 0.02 0.02 0.0205 0.0335 0.058 0.0845 0.098 0.152 0.1805 0.234 0.2945 0.3 0.3

106.2 113.3 121.8 128 136.4 145.4 152.6 166.6 168 182 184 194.5 200.4 205.7 217.6 225.9 236.1 250 265.5 272.2 283.3 295.7 307.5 318.3 327.6 334.4 341.5 349.8 358.9 366.3 375.1 383.1 391.2 399.4 406.6 412.8

NaN 7.1 8.5 6.2 8.4 9 7.2 14 1.4 14 2 10.5 5.9 5.3 11.9 8.3 10.2 13.9 15.5 NaN 17.8 12.4 11.8 10.8 9.3 6.8 7.1 8.3 9.1 7.4 8.8 8 8.1 8.2 7.2 6.2

NaN NaN NaN NaN NaN 193.28 167.23 154.18 156.61 181.11 191.62 244.58 278.22 311.9 411.88 495.53 614.63 704.88 743.42 748.48 742.57 670.24 555.57 450.54 386.46 329.82 251.25 170.45 115.43 84.31 60.62 45.23 34 26.29 22 19.6

0 5 11 16 21 27 33 38 44 49 54 61 66 71 77 82 87 94 101 NaN 108 113 118 123 129 135 140 145 150 156 160 166 171 176 181 186

METTLER TOLEDO

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Titration Application M459-2010

Instruments

- DL58 with manual addition of SnCl2 solution - AT261 Balance
This method can also be run with the following instruments: - DL55/DL58 (2 DV090 burettes drives) and DL70ES/77 instruments (4 DV090 burette drives) - DL50/DL53, DL67 (manual addition of SnCl2 solution, phosphoric and sulphuric acids).

Accessories

- 2 x 10 mL DV1010 burettes - Glass titration beaker ME-101446 - LabX titration pro

Results (DL58)
METTLER TOLEDO DL58 V2.4 DL58 Fumehood Method: Fe003 Iron in Results Series start time 08-Jun-05 4:48 PM No. Note / ID Start time Rx 1 Fe2O3 08-Jun-05 4:48 PM R1 = R3 = R4 = 2 Fe2O3 08-Jun-05 6:09 PM R1 = R3 = R4 = 3 Fe2O3 08-Jun-05 6:36 PM R1 = R3 = R4 = 4 Fe2O3 08-Jun-05 7:10 PM R1 = R3 = R4 = Statistics: 64.285 ± 0.586% , srel: 0.912%

Iron Ore

08-Jun-05 11:46 AM

Result 1.514 12.215 64.334 1.452 10.509 63.499 1.363 10.300 64.389 1.284 11.341 64.917

Unit mL mL % mL mL % mL mL % mL mL %

Name Consumption Consumption Iron Content Consumption Consumption Iron Content Consumption Consumption Iron Content Consumption Consumption Iron Content

Titration curve (DL58)

METTLER TOLEDO

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Titration Application M459-2010

Table of measured values (DL58)
Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s -------------------------------------------------------------------------------------------ET1 0.0000 103.9 0:06 0.0200 0.0200 118.1 14.2 707.6 0:17 0.0400 0.0200 114.9 -3.2 -158.3 0:47 0.0600 0.0200 118.3 3.4 168.0 1:18 0.1050 0.0450 142.0 23.7 527.0 1:48 0.1250 0.0200 149.0 7.0 352.2 2:17 0.1700 0.0450 204.7 55.7 1237.8 2:30 0.1900 0.0200 221.6 16.9 846.5 2:36 EQP1 0.2100 0.0200 250.6 29.0 1447.5 2:51 0.2300 0.0200 266.9 16.3 817.4 2:59 0.2720 0.0420 290.9 24.0 570.8 3:04 0.2960 0.0240 298.7 7.8 325.8 3:10 0.3440 0.0480 310.9 12.1 253.1 3:15 0.3880 0.0440 317.9 7.0 160.1 3:21 . . . . . . . . . . . . . . . . . . 11.3680 0.0890 541.0 8.8 98.7 7:51 11.4310 0.0630 549.1 8.1 128.2 7:56 11.4810 0.0500 558.3 9.2 184.8 8:02 11.5140 0.0330 566.0 7.7 233.0 8:07 11.5420 0.0280 576.0 10.0 355.4 8:14 11.5620 0.0200 583.5 7.5 374.8 8:19 11.5820 0.0200 599.0 15.5 775.4 8:25 11.6020 0.0200 625.1 26.1 1305.4 8:32 EQP2 11.6220 0.0200 833.9 208.8 10439.2 9:02 11.6420 0.0200 838.0 4.1 206.8 9:14 11.6620 0.0200 839.6 1.6 80.8 9:19 11.6860 0.0240 841.9 2.3 96.9 9:32 11.7340 0.0480 843.4 1.5 31.0 9:39 11.7830 0.0490 843.9 0.5 10.6 9:47 11.8810 0.0980 845.8 1.9 19.1 9:53 12.0770 0.1960 847.9 2.1 10.6 10:00 12.3770 0.3000 850.0 2.1 7.1 10:06 12.6770 0.3000 852.0 2.0 6.7 10:15

Comments and Methods
Chemical reactions: 1. Fe3+ has first to be reduced to Fe2+. This is achieved by adding a concentrated solution of stannous chloride, SnCl2 according to the equation: 2 Fe3+ + Sn2+ → 2 Fe2+ + Sn4+ SnCl2 can be added manually until the solution becomes colorless, or it can be added using an endpoint titration function. The titration is stopped at the potential achieved when the solution becomes colorless. To determine this value, it is first necessary to measure the potential after manual addition. Afterwards, this value is entered as absolute EP in the titration method. 2. Iron can be now titrated with potassium dichromate, K2Cr2O7. This titration leads to two equivalence points according to the following reactions: - 1st EQP:
nd

Excess SnCl2 arising from the EP titration is oxidized with potassium dichromate. 3 Sn2+ + 6 Fe2+ + Cr2O722+

+

14 H+ 14 H+

3 Sn4+ + 6 Fe3+ +

2 Cr3+ + 2 Cr3+ +

7 H2O

- 2 EQP: Oxidation of Fe

with potassium dichromate. + → 7 H2O

Cr2O72-

METTLER TOLEDO

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Titration Application M459-2010

Tx Titrator
Method MS1055 Version Fe(II) in Ore (Rondo) 24-03-2010 14:45

001 - Title Type ............................... Compatible with .................... Method ID .......................... Title .............................. Author ............................. Date/time .......................... Modified on ........................ Modified by ........................ Protect ............................ SOP ................................ 002 - Sample Number of IDs ...................... ID1 .............................. Entry type ......................... Lower limit [g] .................. Upper limit [g] .................. Density [g/mL] ................... Correction factor ................ Temperature [°C] ................. Entry ............................ 003 – Titration stand (Rondo/Tower A) Type ............................... Titration stand .................... Lid handling ....................... 004 – Stir Speed [%] .......................... Duration [s] ....................... Condition .......................... 005 – Titration (EP) [1] Titrant Titrant .......................... Concentration [mol/L] ............ Sensor Type ............................. Sensor ......................... Unit. .......................... 006 - Temperature acquisition Temperature acquisition .......... Stir Speed [%] ........................ Predispense Mode ............................. Wait time [s] .................... Control Mode ............................. Tendency ......................... End point value [mV] ............. Control band [mV] ................ Dosing rate (max) [mL/min] ....... Dosing rate (min) [μL/min] ....... Termination At EP ............................ Termination delay [s] ............ At Vmax [mL] ..................... Max. time [s] .................... Accompanying stating Accompanying stating ............. Condition Condition ........................ 007 - Calculation R1 Result ............................. Result Unit ........................ Formula ............................ Constant C= ........................ M .................................. z .................................. Decimal places ..................... Result limits ...................... Record statistics .................. Extra statistical functions ........ Send to buffer ..................... Condition .......................... 008 - Stir Speed [%] .......................... Duration [s] ....................... Condition .......................... 009 – Dispense (normal) [1] Titrant ............................ Concentration ...................... Volume [mL] ........................ Dosing rate [mL/min] ............... Condition .......................... 010 – Dispense (normal) [2] Titrant ............................ Concentration ......................

General titration T70/90 MS1055 Fe(II) in Ore (Rondo) wahlen 24.03.2010 11:53 24.04.2010 14:22 wahlen No None 1 Iron Ore Weight 0.08 0.15 1.0 1.0 25 Arbitrary Rondo/RondoA Rondo60/1A No 50 15 No

SnCl2 1.0 mV DMi140-SC mV No 45 None s Absolute Negative 120 350 7 10 Yes 0 15.0 infinity No No EP Consumption mL R1=VEQ 1 M[None] z[None] 3 No Yes No No No 50 2 No Conc H3PO4 16 3.0 40 No Conc H2SO4 18

Volume [mL] .........................3.0 Dosing rate [mL/min] ................20 Condition ...........................No 011 - Stir Speed [%] ...........................50 Time [s] ............................15 Condition ...........................No 012 – Titration (EQP) [2] Titrant Titrant ...........................1/6 K2Cr2O7 Concentration [mol/L] .............0.1 Sensor ..............................DM140 Type ..............................mV Sensor ..........................DMi140-SC Unit ............................mV Temperature acquisition Temperature acquisition ...........No Stir Speed [%] .........................45 Predispense Mode ..............................None Wait time [s] .....................0 Control Control ...........................User Titrant addition ................Dynamic dE (set value) [mV] .............8.0 dV (min) [mL] ...................0.02 dV (max) [mL] ...................0.3 Mode ..............................Equilibrium controlled dE [mV] .........................0.5 dt [s] ..........................1.0 t(min)[s] .......................5 t(max)[s] .......................30 Evaluation and recognition Procedure .........................Standard Threshold [mV/mL] .................150 Tendency ..........................Positive Ranges ............................1 Lower limit 1 [mV] ................150 Upper limit 1 [mV] ................2000 Add. EQP criteria .................No Termination At Vmax [mL] ......................10.0 At potential ......................No At slope ..........................No After number of recognized EQPs ...Yes Number of EQPs ..................2 Combined termination criteria .....Yes Accompanying stating Accompanying stating ..............No Condition Condition .........................No 013 – Calculation R2 Result ..............................2nd EQP Consumption Result Unit .........................mL Formula .............................R2=VEQ2[2] Constant C= .........................1 M ...................................M[None] z ...................................z[None] Decimal places ......................3 Result limits .......................No Record statistics ...................Yes Extra statistical functions .........No Send to buffer ......................No Condition ...........................No 014 – Calculation R3 Result ..............................Iron Content Result Unit .........................% Formula .............................R3=Q2[2]*C/m Constant C= .........................M/10*z) M ...................................M[Iron] z ...................................z[Iron] Decimal places ......................3 Result limits .......................No Record statistics ...................Yes Extra statistical functions .........No Send to buffer ......................No Condition ...........................No 015 - Rinse Auxiliary reagent ...................Water Tower A Rinse cycles ........................1 Vol. per cycle [mL] .................10 Position ............................Current position Drain ...............................No Condition ...........................No 016- End of sample

Note:
The method can be easily used with a T50 titrator: - Delete either calculation R1 or calculation R2 - Use a “Dispense” function instead of an EP titration

METTLER TOLEDO

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Titration Application M459-2010

DL5x Titrator
Method Fe003 Version Iron in Iron ore 08-Jun-2005 11:46

Title Method ID .......................... Title .............................. Date/time .......................... Sample Sample ID .......................... Entry type ......................... Lower limit [g] ................ Upper limit [g] ................ Molar mass M ....................... Equivalent number z ................ Titration stand .................... Temperature sensor ................. Stir Speed [%] .......................... Time [s] ........................... EP titration Titrant/Sensor Titrant ........................ Concentration [mol/L] .......... Sensor ......................... Unit of meas. .................. Predispensing ...................... Titrant addition ................... dE(set) ........................ dV(min) [mL] ................... dV(max) [mL] ................... dE [mV] ........................ dt [s] ......................... t(min) [s] ..................... t(max) [s] ..................... Endpoint Potential[mV,pH,…] ............. Tendency Tendency ....................... Termination Maximum volume [mL] ............ Delay[s] ....................... Calculation Formula ........................... Constant ........................... Decimal places ..................... Result unit ........................ Result name ........................ Statistics ........................ Calculation Formula ........................... Constant ........................... Decimal places ..................... Result unit ........................ Result name ........................ Statistics ........................ Report Output unit ....................... Results ............................ All results ........................ Raw results ........................ Table of measured values ........... Sample data ........................ E - V curve ........................ dE/dV – V curve .................... d2E/dV2 – V curve ................... log dE/dV – V curve... ............. E – t curve ........................ V – t curve ........................ dV/dt - t curve ................... Instruction Text ............................... ............................... Text ............................... Text ............................... Stir Speed [%] .......................... Time [s] ........................... EQP titration Titrant/Sensor Titrant ........................ Concentration [mol/L] .......... Sensor ......................... Unit of meas. .................. Predispensing ...................... Volume [mL] .................... Wait time [s] .................. Titrant addition ................... dE(set) ........................ dV(min) [mL] ...................

Fe003 Iron in Iron ore 08-Jun-2005 11:46 Fe2O3 Weight 0.08 0.15 55.85 1 Stand 1 Manual 50 15

SnCl2 1.0 DM140 mV No Dynamic 8.0 0.02 0.15 1.0 1.0 2.0 20.0 120 Negative 5.0 10 R=VEQ 3 mL Consumption No

0 No Yes Computer No No No No No No No No No No No No Add 3mL of conc. phosphoric acid followed by 3mL of conc sulphuric acid!!! 50 15

dV(max) [mL] ....................0.3 Measure mode ........................Equilibrium controlled dE [mV] .........................0.5 dt [s] ..........................1.0 t(min) [s] ......................5.0 t(max) [s] ......................30.0 Recognition Threshold .......................400.0 Steepest jump only ..............No Range ...........................Yes Limit A [mV, pH,…] ...........200 Limit B [mV, pH,…] ...........2000 Tendency ........................Positive Termination at maximum volume [mL] ..........30.0 at potential ....................No at slope ........................Yes Slope [mV, pH, …/mL] .......10.0 after number EQPs ...............Yes n = .......................2 comb. termination criteria ......Yes Evaluation Procedure .......................Standard Potential 1 ....................No Potential 2 ....................No Stop for reevaluation ..........No Calculation Formula ............................R3=VEQ2[2] Constant ............................C3=1 Decimal places ......................3 Result unit .........................mL Result name .........................Consumption Statistics .........................No Calculation Formula ............................R4=Q2[2]*C4/m Constant ............................C4=M/(10*z) Decimal places ......................3 Result unit .........................% Result name .........................Iron content Statistics .........................Yes Report Output unit ........................Computer Results .............................No All results .........................No Raw results .........................No Table of measured values ............No Sample data .........................No E - V curve .........................No dE/dV – V curve .....................No d2E/dV2 – V curve ....................No log dE/dV – V curve... ..............No E – t curve .........................No V – t curve .........................No dV/dt - t curve ....................No

1/6 K2Cr2O7 0.1 DM140 mV to volume 0.2 20 Dynamic 8.0 0.02

METTLER TOLEDO

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Titration Application M459-2010

METTLER TOLEDO
Determination of Total Iron Content of Iron Ores

Application M622-2010

The iron content in 60-65% iron ores is titrated with potassium dichromate K2Cr2O7 in strong acid solution after reduction with tin(II) and titanium(III). The potential change is monitored by a combined platinum ring redox sensor.

Sample

Iron ores, 0.15 - 0.25 g 60-65% iron content Iron, Fe M = 55.85; z = 1

Preparation and Procedures
CAUTION: Work in a fume hood, use safety goggles and wear gloves. Sample dissolution:
- 0.15-0.25 g iron ore is placed in a glass titration beaker for dissolution. - Place sample beaker in a fume hood. - Add 1 m 10% SnCl2 with a pipette. - Add 20 mL concentrated HCl and swirl the beaker after addition to ensure complete mixing. - Place beaker on a hot plate set at 125-150°C with integrated magnetic stirrer. Cover it with a clean watch glass and start digestion of the ore. - After 10-20 min, swirl beaker to break up any agglomerated particles. - Digest for a minimum of 40 min in total. - After ore digestion, slightly tilt the beaker and add a magnetic stirrer bar. Place beaker onto the hot plate. Set temperature to heat sample but avoid boiling. Switch stirrer on, ensuring not to loose any sample. - While gently stirring, add dropwise 10% SnCl2 solution until the color turns into a pale straw yellow. If too much SnCl2 is added, i.e. if the solution becomes colorless, add dropwise KMnO4 solution to restore the pale yellow color. - From now on, the sample has to be titrated within 30 min at latest. - Add dropwise 1% TiCl3 solution until liquid turns colorless. Then add three additional drops. - Add 5 mL 0.1 M perchloric acid (HClO4). - Wait during 5 s (heating, not boiling), then remove from hot plate. - Add 40 mL deionized water, rinsing the inside wall of the beaker. - The sample is ready for titration.

Compound

Chemicals

30-34% Hydrochloric acid, HCl 10% Stannous chloride sol., SnCl2
0.4% Potassium permanganate, KMnO4 1% Titanium trichloride, TiCl3 0.1 mol/L Perchloric acid, HClO4 Deionized water

Titrant

Potassium dichromate, K2Cr2O7 c(1/6 K2Cr2O7) = 0.1 mol/L Ammonium ferrous sulfate, (NH4)2Fe(SO4)2 Combined redox Pt-electrode e.g. DMi140-SC
Reduction to Fe(II): 2 Fe3+ + Sn2+ → 2 Fe2+ + Sn4+ Titration: 2 Fe2+ + 2 Fe3+ +
2-

Standard Indication

Chemistry

Cr2O7 2 Cr3+

+ 14 H+ + 7 H2O

Calculation

Content • R1 = Q*C/m • C = M/(10*z)

Titration:
- Add the prepared titration beakers on the sample changer rack.

- Start titration with potassium dichromate.

Remarks Waste disposal
Neutralize the sample with sodium hydroxide before final disposal as special waste (Chromium).
Li Pei, MT-China, April 1999 Revised March 2010 / C. De Caro

- The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample. - Rinse the electrode after each sample. If necessary, clean the metal ring of the electrode with a paper tissue at the end of a sample series.

Author, Version
METTLER TOLEDO

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Titration Application M622-2010

Instruments

- DL58 Titrator - AG245 Balance
This method can also be run with the G20 and T50/70/90 Titration Excellence (minor adaptations in their method), and with the DL50/DL53/DL55, and DL67/70ES/77 titrators.

Accessories

-

1 x 10 mL DV1010 burette Glass titration beaker ME-101446 Sample Changer with pump (e.g. Rondo20) Printer (EPSON SC 600)

Results
METTLER TOLEDO DL58 Titrator V2.0 MTCS ANA MS Application Lab 12-Apr-1999 16:57

Method Measured User ALL RESULTS No. 1 2 3 ID Iron Iron Iron

10150 Iron in iron ores 13-Apr-1999 11:46 Li Pei

Sample size and results 0.0995 R1 = 64.7050 0.1063 R1 = 64.7105 0.1004 R1 = 64.8998 g % g % g %

iron content iron content iron content

STATISTICS Number results R1 Mean value Standard deviation Rel. standard deviation

n x s srel

= = = =

3 64.7718 0.11093 0.171

% % %

iron content iron content

Titration curve

METTLER TOLEDO

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Titration Application M622-2010

Table of measured values
Not available

Comments and Methods
1. This method is based on a national standard pretreatment method for the determination of total iron content in iron ores (China, GB 6730.5-86, “The chemistry analysis process for the iron ore and the capacity process for measuring the amount of the whole iron with titanium trichloride and potassium dichromate”, see also ISO 2597-1:2006, ISO 2597-2:2008, and ISO 9507:1990). Samples must be analyszed within 30 min after the 2nd addition of 10% stannous chloride SnCl2 solution. A sample changer is used in this method for a fully automated procedure. The method can be easily modified for manual operation: enter “Stand 1” as titration stand in the function Sample (DL5x, DL7x) or “Manual Stand” (Titration Excellence). After each sample, the sensor is rinsed with deionized water by means of a peristaltic pump connected to the sample changer. During dissolution, iron is oxidized to Fe3+. In order to be titrated with potassium dichromate, Fe3+ has to be reduced to Fe2+. This is achieved by adding a concentrated solution of stannous chloride, SnCl2 according to the equation: 2 Fe3+ + Sn2+ → 2 Fe2+ + Sn4+ Excess SnCl2 is oxidized with potassium permanganate, KMnO4, according to: 5 Sn2+ + 2 MnO4- + 16 H+ → 5 Sn4+ + 2 Mn2+ + 8 H2O In the sample all iron is present as Fe2+. However, if the prepared sample solution is exposed too long a time to air, Fe2+ is easily oxidized by oxygen to Fe3+. To avoid it, some titanium trichloride, TiCl3, is added in slight excess: Ti3+ + Fe3+→ Fe2+ + Ti4+ Perchloric acid, HClO4, is added to neutralize excess TiCl3 . 2. Iron can be now titrated with potassium dichromate, K2Cr2O7, according to the following reaction: 6 Fe2+ + Cr2O72- + 14 H+ → 6 Fe3+ + 2 Cr3+ + 7 H2O

2. 3.

4.

Chemical reactions: 1.

Literature: 1. 2. 3. 4. ISO 2597-1:2006, “Iron ores -- Determination of total iron content -- Part 1: Titrimetric method after tin(II) chloride reduction”. ISO 2597-2:2006, “Determination of total iron content -- Part 2: Titrimetric methods after titanium(III) chloride reduction”. ISO 9507:1990, “Determination of total iron content -- Titanium(III) chloride reduction methods” S. Kallmann, E. Kormanova, “Pollution-free method for the determination of iron in iron ore”, Talanta, Vol. 29(8), 1982, pp. 700-702. J. Henry, R. Gelbach, “Dichromate determination of iron using silver reductor”, Ind. Eng. Chem. Anal. Ed., Vol. 16 (1), 1944, p. 49.

5.

METTLER TOLEDO

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Titration Application M622-2010

DL5x Titrator Method 10150 Version Iron in iron ores 12-Apr-1999 16:57

Titration Excellence 001 Title Type General titration Compatible with T50 / T70 / T90 ID 10150 Title Iron in iron ores Author METTLER TOLEDO Date/Time 01.03.2010 15:00:00 Modified -Modified by -Protect No SOP None 002 Sample Number of IDs 1 ID 1 Iron Entry type Weight Lower limit 0.05 g Upper limit 0.15 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C 003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Stir Speed 35% Duration 15 s 005 Titration (EQP) [1] Titrant Titrant 1/6 K2Cr2O7 Concentration 0.1 mol/L Sensor Type mV Sensor DMi140-SC Unit mV Temperature acquisition Temperature acquisition No Stir Speed 35% Predispense Mode Volume Volume 3.0 mL Wait time 10 s Control Control User Titrant addition Dynamic dE(set) 4.0 dV(min) 0.02 mL dV(max) 0.15 mL Meas. val. acquisition Equilibrium controlled dE 1.0 mV dt 1.0 s t(min) 6.0 s t(max) 25.0 s Evaluation and recognition Procedure Standard Threshold 200 mV/mL Tendency Positive Ranges 0 Add. EQP criteria No Termination At Vmax 20.0 mL At potential No At slope No After number of recognized EQPs Yes Number EQPs 1 Combined termination criteria No 006 Calculation R1 Result iron content Result unit % Formula R=Q*C/m Constant C=M/(10*z) M M[Iron] z z[Iron] Decimal places 4 Result limits No Record statistics Yes Extra statistical functions No Send to buffer No 007 Record Summary Yes Results Per sample Raw results Per sample Table of meas. Values Per sample . . . 008 End of sample

Title Method ID .......................... Title .............................. Date/time .......................... Sample Sample ID .......................... Entry type ......................... Lower limit [g] ................ Upper limit [g] ................ Molar mass M ....................... Equivalent number z ................ Titration stand .................... Pump ........................... Pump ........................... Rinse .......................... Solvent ...................... Volume [mL] .................. Conditioning ................... Temperature sensor ................. Stir Speed [%] .......................... Time [s] ........................... EQP titration Titrant/Sensor Titrant ........................ Concentration [mol/L] .......... Sensor ......................... Unit of meas. .................. Predispensing ...................... Volume [mL] .................... Wait time [s] .................. Titrant addition ................... dE(set) ........................ dV(min) [mL] ................... dV(max) [mL] ................... Measure mode ....................... dE [mV] ........................ dt [s] ......................... t(min) [s] ..................... t(max) [s] ..................... Recognition Threshold ...................... Steepest jump only ............. Range .......................... Tendency ....................... Termination at maximum volume [mL] ......... at potential ................... at slope ....................... after number EQPs .............. n = ...................... comb. termination criteria ..... Evaluation Procedure ...................... Potential 1 ................... Potential 2 ................... Stop for reevaluation ......... Calculation Formula ........................... Constant ........................... Decimal places ..................... Result unit ........................ Result name ........................ Statistics ........................ Calculation Formula ........................... Constant ........................... Decimal places ..................... Result unit ........................ Result name ........................ Statistics ........................ Report Output unit ....................... Results ............................ All results ........................ Raw results ........................ Table of measured values ........... Sample data ........................ E - V curve ........................ dE/dV – V curve .................... d2E/dV2 – V curve ................... log dE/dV – V curve... ............. E – t curve ........................ V – t curve ........................ dV/dt - t curve ...................

10150 Iron in iron ores 12-Apr-1999 16:57 Iron Weight 0.05 0.15 55.85 1 ST20A 1 No No Yes H2O 15.0 No Manual 50 15

1/6 K2Cr2O7 0.1 DM140 mV to volume 3.0 10 Dynamic 4.0 0.02 0.15 Equilibrium controlled 1.0 1.0 6.0 25.0 200.0 No No Positive 20.0 No No Yes 1 No Standard No No No R1=Q*C1/m C1=M/(10*z) 4 % iron content Yes

0

No Printer Yes Yes No Yes No Yes Yes No No No No No

METTLER TOLEDO

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Titration Application M622-2010

METTLER TOLEDO

Application M060-2010

Determination of Iron (Fe(II) ) and Sulphuric Acid (H2SO4)
Potentiometric determination of iron(II) by redox titration with potassium dichromate, K2Cr2O7, and of sulphuric acid by back titration of excess sodium hydroxide with hydrochloric acid. The potential is monitored by a combined platinum ring electrode (Fe), and a combined pH glass electrode (H2SO4).

Sample

Fe(II)/H2SO4 aqueous solution, 5 mL
c(H2SO4) = approx. 5% c(Fe) = approx. 6-7 g/L Fe(SO4)*7H2O

Preparation and Procedures
CAUTION: Use safety goggles and wear gloves. Sample preparation: - 3-4 g FeSO4*7H2O (M = 278.02) is dissolved in a 500 mL volumetric flask with 150-200 mL 5% sulfuric acid solution. - Shake the flask to dissolve iron sulfate, and fill up to the mark with 5% H2SO4 solution. - Pipette 5 mL into a titration beaker. Titration: Four methods are used to determine Fe(II)/H2SO4. The method sequence is the following: 1) 060 2) 060C 3) 060A 4) 060B

Compound

Iron, Fe M = 55.85; z = 1 Sulfuric acid, H2SO4 M = 98.08; z = 2 5% sulfuric acid, H2SO4 Deionized water

Chemicals

Titrant

Potassium dichromate, K2Cr2O7 c(1/6 K2Cr2O7) = 0.1 mol/L Hydrochloric acid, HCl, 0.1 mol/L Sodium hydroxide, NaOH, 0.1 mol/L

Standard Indication

For K2Cr2O7: (NH4)2Fe(SO4)2 For HCl: THAM (TRIS)
Redox Pt-electrode, DMi140-SC pH glass electrode, DGi111-SC

- Method 060 (Fe-determination): Fe(II)-Titration with K2Cr2O7. The pH value has to be between 2 and 3 to avoid oxidation of Fe(II). The result is multiplied by 2 (see “Chemistry”) and stored as auxil. value H2 to be used in method 060B. - Method 060C (Back value determination): The exact amount of NaOH added to the sample is determined by titration with HCl. This value is stored as auxiliary value H3, and is used in method 060B. - Method 060A (Sample preparation): Addition of 10 mL 0.1 mol/L NaOH to the Fe(II)solution. H2SO4 and Fe(II) reacts with NaOH (see “Chemistry”). Since the reaction between Fe and OH--ions is slow, a conditioning time of 1200 s has been defined in the method.

Chemistry

Titration Fe(II): 2 Fe2+ + 2 Fe
3+

Cr2O72- + 14 H+ 2 Cr
3+

+

+ 7 H2O

Reaction with NaOH: Fe2+ + 2 NaOH → Fe(OH)2 + 2 Na+ H2SO4 +2 NaOH→Na2SO4 + H2O Titration excess NaOH: HCl + NaOH → NaCl + H2O

- Method 060B (Acid determination):
A direct titration of H2SO4 is not possible since Fe(II) also reacts with NaOH. After addition of a known amount of NaOH, excess NaOH in the previously prepared samples (060A) is determined by back-titration with HCl. The difference between the sum (Fe + H2SO4) and Fe(II)-content (060) gives the H2SO4 content.

Calculation

060 : Content Fe(II), g/L • R = Q*C/m, C = M/z 060B: Content H2SO4 g/L • R = Q*C/m, C = M/z For DL7x : replace m with U (volume)

Remarks
- The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample. - The electrode is rinsed after each sample with water.

Waste disposal Author, Version
METTLER TOLEDO

Neutralize the sample before final disposal as special waste (Chromium).
Maria-José Schmid, MSG, Oct 1991 Revised March 2010 / C. De Caro

Page 1 of 10

Titration Application M060-2010

Instruments

- DL70 Titrator - AT250 Balance
This method can also be run with the T50/70/90 Titration Excellence, with the DL70ES/77 titrators, and with the DL5x and DL67 instruments (manual exchange of burettes).

Accessories

-

3 x 10 mL DV1010 burette 2 x additional DV090 burette drive Sample Changer, i.e. Rondo 20 with pump Titration beaker ME-101974

Results (Back-value, Fe-determination)
060C Back value Oct/18/1991 12:30 SW Version 2.0 RESULTS No Identification 1/1 NaOH 1/2 NaOH 1/3 NaOH measured Titrator User Oct/18/1991 P100 mjs 12:56

Volume 12.0 10.0 10.0

mL mL mL

Results 1.031 mmol 1.030 mol/L 1.030 mol/L

Back value mol/L mol/L

STATISTICS Number results R1 Mean value Standard deviation Rel. standard deviation Outlier test: no outliers!

n x s srel

= = = =

3 1.030 0.0001 0.006

mmol mmol %

Back value Back value

AUXILIARY VALUE New value H3 = 1.030455 Back value NaOH ============================================================================================================= 060 Fe(II) determination measured Oct/01/1991 14:43 Oct/01/1991 11:53 Titrator P100 SW Version 2.0 User mjs RESULTS No Identification 1/1 1/2 1/3 1/4 1/5 1/6 1/7 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4

Volume 10.0 10.0 10.0 10.0 10.0 10.0 10.0 mL mL mL mL mL mL mL

Results 0.0467 6.487 0.0468 6.504 0.0468 6.508 0.0468 6.511 0.0468 6.501 0.0469 6.517 0.0466 6.483 7 0.0468 0.00009 0.193 % mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) Fe(II) mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L

STATISTICS Number results R1 Mean value Standard deviation Rel. standard deviation Outlier test: no outliers! STATISTICS Number results R2 Mean value Standard deviation Rel. standard deviation Outlier test: no outliers! AUXILIARY VALUE New value

n x s srel

= = = =

mol/L mol/L

Fe(II) mol/L Fe(II) mol/L

n x s srel

= = = =

7 6.502 0.0126 0.193

g/L g/L %

Fe(II) g/L Fe(II) g/L

H2

= 0.04677

Fe

METTLER TOLEDO

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Titration Application M060-2010

Titration curve (Fe-determination)

Sample 1/7

Table of measured values (Fe-determination)

Sample 1/7

METTLER TOLEDO

Page 3 of 10

Titration Application M060-2010

Comments
1. Both ferrous ion (Fe2+) and sulfuric acid (H2SO4) react with sodium hydroxide to Fe(OH)2, a solid precipitate, and to water and sodium sulfate. Thus, a direct titration of sulfuric acid is not possible when iron ions (Fe2+ and Fe3+ are present in the sample solution. In addition, the reaction between ferrous ions, Fe2+, and hydroxide ions, OH-, is quite slow. Therefore, a direct titration of Fe2+ with sodium hydroxide is not suitable for titration analysis. For this reason, a back titration with a long waiting time after dispensing excess sodium hydroxide is the method of choice. First, the back value of 10 mL 0.1 M sodium hydroxide is determined with hydrochloric acid (Method 060C). The result is stored as auxiliary value H3. Note that the pH glass electrode has to be adjusted using pH buffer solutions. Subsequently, iron is selectively determined in the sample solution by redox titration with potassium dichromate as a titrant, K2Cr2O7 (Method 060). The result is multiplied by two (equivalence no. z = 2 for this reaction), it is expressed as FeSO4*7H2O, and stored as auxiliary value H2. 6 Fe2+ + Cr2O72- + 14 H+ → 6 Fe3+ + 2 Cr3+ + 7 H2O

2.

3.

4.

The pH value of the sample solution (5 mL + 50 mL deionized water) has to be between 2 and 3. 5. Method 060A allows for sample preparation: 10 mL 0.1 M NaOH is added to the sample (5 mL) and a waiting time of 1200 s is defined to achieve complete reaction with iron ions. Subsequently, this sample is analyzed by back-titration of excess NaOH with hydrochloric acid (Method 060B) to get the sulfuric acid content.

6.

Results (H2SO4-determination)
060B Acid determination Oct/22/1991 10:35 SW Version 2.0 RESULTS No 1/1 1/2 1/3 1/4 1/5 1/6 1/7 Identification Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Fe+H2SO4 Volume 5.0 5.0 5.0 5.0 5.0 5.0 5.0 mL mL mL mL mL mL mL Results 0.0969 2.4563 0.0970 2.4588 0.0974 2.4817 0.0971 2.4654 0.0979 2.5059 0.0973 2.4767 0.0973 2.4753 mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L Total sum Acid content Total sum Acid content Total sum Acid content Total sum Acid content Total sum Acid content Total sum Acid content Total sum Acid content measured Titrator User Oct/22/1991 P100 mjs 12:11

STATISTICS Number results R2 Mean value Standard deviation Rel. standard deviation Outlier test: no outliers!

n x s srel

= = = =

7 2.4743 0.01684 0.681

g/L g/L %

Acid content Acid content

METTLER TOLEDO

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Titration Application M060-2010

Titration curve (H2SO4-determination)

Sample 1/7

Table of measured values (H2SO4-determination)

Sample 1/7

METTLER TOLEDO

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Titration Application M060-2010

DL70 Titrator
Method 060C Version Back value 18-Oct-1991 Method 12:30 060 Version Fe(II) determination 01-Oct-1991 11:53

Title Method ID .......................... Title .............................. Date/time .......................... Sample Number samples ..................... Titration stand .................... Entry type ......................... Volume [mL] .................... ID ................................. Molar mass M ....................... Equivalent number z ................ Dispense Titrant ........................... Concentration [mol/L] .............. Volume [mL] ........................ Stir Speed [%] .......................... Time [s] ........................... Titration Titrant ............................ Concentration [mol/L] .............. Sensor ............................. Unit of meas. ...................... Titration mode ..................... Predispensing 1 ................ Volume [mL] .................. Predispensing 2 ................ Potential [mV,pH, …] ......... Titrant addition ............... dE(set)[mV] .................. Limits dV .................... dV(min) [mL] .............. dV(max) [mL] .............. Measure mode ................... dE [mV] ...................... dt [s] ....................... t(min) [s] ................... t(max) [s] ................... Threshold ...................... Maximum volume [mL] ............ Termination after n EQPs ....... n = ......................... Evaluation procedure ........... Rinse Auxiliary reagent .................. Volume [mL] ........................ Calculation Result name ....................... Formula ............................ Constant ........................... Result unit ........................ Decimal places ..................... Statistics Ri (i=index) ....................... Standard deviation s ............... Rel. standard deviation srel ....... Auxiliary value ID text ............................ Formula ............................ Record Output unit ....................... Results last sample ................ All results ........................ Conditioning Interval ........................... Time [s] ...........................

060C Back value 18-Oct-1991

12:30

3 ST20 Fixed volume U 10.0 NaOH 40.0 1 NaOH 0.1 10.0 50 10 HCl 0.1 DG111-SC as installed EQP mL 5.0 To potential 10.0 DYN 8.0 Absolute 0.02 0.2 EQU 1.0 1.0 2.0 20.0 10.0 15.0 Yes 1 Standard H2O 10.0 Back value R=Q mmol 3 R1 Yes Yes Back value NaOH H3=x Printer Yes No 1 10

Title Method ID ...........................060 Title ...............................Fe(II) determination Date/time ...........................01-Oct-1991 11:53 Sample Number samples ......................3 Titration stand .....................ST20 Entry type ..........................Fixed volume U Volume [mL] .....................10.0 ID ..................................Fe+H2SO4 Molar mass M ........................278.02 Equivalent number z .................1 Stir Speed [%] ...........................50 Time [s] ............................10 Titration Titrant .............................1/6 K2Cr2O7 Concentration [mol/L] ...............0.1 Sensor ..............................DM140-SC Unit of meas. .......................mV Titration mode ......................EQP Predispensing 1 .................mL Volume [mL] ..................0.5 Titrant addition ................DYN dE(set)[mV] ..................8.0 Limits dV ....................Relative dV(min) [%dosVol] ..........0.5 dV(max) [%buVol] ...........5.0 Measure mode ....................EQU dE [mV] ......................0.5 dt [s] .......................1.0 t(min) [s] ...................2.0 t(max) [s] ...................20.0 Threshold .......................200.0 EQP range .......................Yes Limit A [mV,pH,…] ............550.0 Limit B [mV,pH,…] ............900.0 Maximum volume [mL] .............10.0 Termination at potential ........Yes Potential [mV, pH, …] ........706.22 Termination after n EQPs ........Yes n = .........................1 Evaluation procedure ............Standard Steepest jump only ..............Yes Calculation Result name ........................Fe(II) mol/L Formula .............................R=2*(Q*C/U) Constant ............................C=1 Result unit .........................mol/L Decimal places ......................4 Calculation Result name ........................Fe(II) g/L Formula .............................R2=Q*C2/U Constant ............................C2=M/z Result unit .........................mol/L Decimal places ......................4 Rinse Auxiliary reagent ...................H2O Volume [mL] .........................10.0 Record Output unit ........................Printer Sample data .........................Yes Raw results last sample .............Yes Results last sample .................Yes Statistics Ri (i=index) ........................R1 Standard deviation s ................Yes Rel. standard deviation srel ........Yes Outlier test ........................Yes Statistics Ri (i=index) ........................R2 Standard deviation s ................Yes Rel. standard deviation srel ........Yes Outlier test ........................Yes Auxiliary value ID text .............................Fe Formula .............................H2=x[1] Record Output unit ........................Printer Sample data .........................Yes Raw results last sample .............Yes Results last sample .................Yes Table of measured values ............Yes E – V curve .........................Yes dE/dV – V curve .....................Yes

METTLER TOLEDO

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Titration Application M060-2010

Method

060A Version

Sample preparation 22-Oct-1991 10:30

Method

060B Version

Acid determination 22-Oct-1991 10:35

Title Method ID .......................... Title .............................. Date/time .......................... Sample Number samples ..................... Titration stand .................... Entry type ......................... Volume [mL] .................... ID ................................. Molar mass M ....................... Equivalent number z ................ Dispense Titrant ........................... Concentration [mol/L] .............. Volume [mL] ........................ Dispense Titrant ........................... Concentration [mol/L] .............. Volume [mL] ........................ Stir Speed [%] .......................... Time [s] ........................... Measure Sensor ............................. Unit of meas. ...................... dE [mV] ............................ dt [s] ............................. t(min) mode ........................ t(min) [s] ..................... t(max) [s] ......................... Calculation Result name ....................... Formula ............................ Constant ........................... Result unit ........................ Decimal places ..................... Rinse Auxiliary reagent .................. Volume [mL] ........................ Conditioning Interval ........................... Time [s] ........................... Statistics Ri (i=index) ....................... Standard deviation s ............... Rel. standard deviation srel ....... Conditioning Interval ........................... Time [s] ...........................

060A Sample preparation 22-Oct-1991 10:30 7 ST20 Fixed volume U 5.0 Fe+H2SO4+NaOH 0.0 1 Sample 0.1 5.0 NaOH 0.1 10.0 60 60 DG111-SC as installed 0.5 1.0 Fix 3.0 30.0 pH value R=E

Title Method ID ...........................060B Title ...............................Acid determination Date/time ...........................22-Oct-1991 10:35 Sample Number samples ......................7 Titration stand .....................ST20 Entry type ..........................Fixed volume U Volume [mL] .....................5.0 ID ..................................Fe+H2SO4 Molar mass M ........................98.0 Equivalent number z .................2 Stir Speed [%] ...........................60 Time [s] ............................10 Titration Titrant .............................H2SO4 Concentration [mol/L] ...............0.1 Sensor ..............................DM111-SC Unit of meas. .......................As installed Titration mode ......................EQP Predispensing 1 .................mL Volume [mL] ..................1.0 Titrant addition ................DYN dE(set)[mV] ..................8.0 Limits dV ....................Absolute dV(min) [mL] ...............0.02 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 .......................3.0 Maximum volume [mL] .............10.0 Termination after n EQPs ........Yes n = .........................1 Evaluation procedure ............Standard Calculation Result name ........................Total sum Formula .............................R=(H3-Q)*C/U Constant ............................C=1 Result unit .........................mol/L Decimal places ......................4 Calculation Result name ........................Acid content Formula .............................R2=(R-H2)*C2 Constant ............................C2=M/z Result unit .........................g/L Decimal places ......................4 Rinse Auxiliary reagent ...................H2O Volume [mL] .........................10.0 Conditioning Interval ............................1 Time [s] ............................10 Record Output unit ........................Printer Raw results last sample .............Yes Results last sample .................Yes E – V curve .........................Yes Statistics Ri (i=index) ........................R2 Standard deviation s ................Yes Rel. standard deviation srel ........Yes Outlier test ........................Yes Record Output unit ........................Printer Short-form method ...................Yes Sample data .........................Yes Raw results last sample .............Yes All results .........................Yes Table of measured values ............Yes E – V curve .........................Yes dE/dV – V curve .....................Yes Conditioning Interval ............................1 Time [s] ............................10

1 H2O 20.0 1 10 R1 Yes Yes 1 1200

Note: After dispensing of NaOH solution the sample is left onto the sample changer to allow for reaction during 1200 s. The electrode is not left into the high alkaline solution to avoid deterioration of the pH glass membrane with time.

METTLER TOLEDO

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Titration Application M060-2010

Titration Excellence
Back-value determination (H3):
001 Title Type Compatible with ID Title Author Date/Time Modified Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume Density Correction factor Temperature General titration T50 / T70 / T90 060C Back-value METTLER TOLEDO 01.03.2010 15:00:00 --No None

Record statistics Extra statistical functions Send to buffer 008 Auxiliary value Name Formula 009 Record Summary Results Raw results Table of meas. value Sample data Ressource data E – V dE/dV – V log dE/dV – V d2E/dV2 – V BETA – V E – t V – t dV/dt – t T – t E-V & dE/dV-V V-t & dV/dt-t Method Series data 010 End of sample

No No No

H3 Mean[R1]

1 HCl Fixed volume 10.0 mL 1.0 g/mL 1.0 25.0°C

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A 004 Stir Speed Duration 005 Titration (EQP) Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Wait time Control Control Titrant addition dE(set) dV(min) dV(max) Meas. val. acquisition dE dt t(min) t(max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number EQPs Combined termination criteria 006 Rinse Auxiliary reagent Rinse cycles Vol. per cycle Position 007 Calculation R1 Result Result unit Formula Constant M z Decimal places Result limits 35% 10 s

No Per sample Per sample Last titration function No No Last titration function No No No No No No No No No No No No

HCl 0.1 mol/L pH DGi111-SC pH No 35% Volume 5.0 mL 10 s User Dynamic 8.0 0.02 mL 0.2 mL Equilibrium controlled 0.5 mV 1.0 s 3.0 s 30.0 s Standard 10 pH/mL Negative No No 15.0 mL No No Yes 1 No

Water 1 10.0 mL Current position

Back value mL R=Q C=1 M[None] z[None] 3 No

METTLER TOLEDO

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Titration Application M060-2010

Fe(II) determination (H2):
001 Title Type Compatible with ID Title . . . 002 Sample Number of IDs ID 1 Entry type Volume . . . General titration T50 / T70 / T90 060 Fe(II) determination

010 Auxiliary value Name Formula 011 Record Summary Results Raw results Table of meas. value Sample data Ressource data E – V dE/dV – V log dE/dV – V d2E/dV2 – V BETA – V E – t V – t dV/dt – t T – t E-V & dE/dV-V V-t & dV/dt-t Method Series data 012 End of sample 013 Record Summary Results Raw results Ressource data Calibration curve Method Series data

H2 Mean[R1]

1 Fe+H2SO4 Fixed volume 10.0 mL

003 Titration stand (Rondo/Tower A) 004 Stir Speed Duration 005 Titration (EQP) Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Wait time Control Control Titrant addition dE(set) dV(min) dV(max) Meas. val. acquisition dE dt t(min) t(max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number EQPs Combined termination criteria 007 Calculation R1 Result Result unit Formula Constant M z Decimal places . . . 008 Calculation R2 Result Result unit Formula Constant M z Decimal places . . . 009 Rinse Auxiliary reagent Rinse cycles Vol. per cycle Position 35% 10 s

No Per sample Per sample Last titration function No No Last titration function No No No No No No No No No No No No

1/6 K2Cr2O7 0.1 mol/L mV DMi140-SC mV No 35% Volume 0.5 mL 10 s

Yes Yes No No No No No

------------------------------------------------------------User Dynamic 8.0 0.02 mL 0.2 mL Equilibrium controlled 0.5 mV 1.0 s 2.0 s 20.0 s Standard 200 mV/mL Positive No No 10.0 mL No No Yes 1 No

Sample preparation:
001 Title Type General titration Compatible with T50 / T70 / T90 ID 060A Title Sample preparation Author METTLER TOLEDO Date/Time 01.03.2010 15:00:00 Modified -Modified by -Protect No SOP None 002 Sample Number of IDs 1 ID 1 Fe+H2SO4 Entry type Fixed volume Volume 5.0 mL Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C 003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A 004 Dispense (normal) [1] Titrant Sample Concentration 0.1 mol/L Volume [mL] 5.0 005 Dispense (normal) [2] Titrant NaOH Concentration 0.1 mol/L Volume [mL] 10.0 006 Stir Speed 60% Duration 60 s 007 Rinse Auxiliary reagent Water Rinse cycles 2 Vol. per cycle 20.0 mL Position Rinse beaker Drain Yes Drain pump SP250 008 End of sample 009 Conditioning Titration stand Rondo60/1A Position Conditioning beaker Time 1200 s Speed 25%

Fe concentration mol/L R=2*(Q*C)/m C=1 M[None] z[None] 4

Fe concentration g/L R2=Q*C2/m C2=M/z M[FeSO4*7H2O] z[FeSO4*7H2O] 3

Water 1 10.0 mL Current position

METTLER TOLEDO

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Titration Application M060-2010

Acid determination:
001 Title Type Compatible with ID Title Author Date/Time Modified Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume Density Correction factor Temperature General titration T50 / T70 / T90 060B Acid determination METTLER TOLEDO 01.03.2010 15:00:00 --No None

007 Calculation R2 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 008 Rinse Auxiliary reagent Rinse cycles Vol. per cycle Position 009 Conditioning Titration stand Position Time Speed 010 Record Summary Results Raw results Table of meas. value Sample data Ressource data E – V dE/dV – V log dE/dV – V d2E/dV2 – V BETA – V E – t V – t dV/dt – t T – t E-V & dE/dV-V V-t & dV/dt-t Method Series data 011 End of sample

Acid content g/L R2=(R1-H[H2])*C2 C=M/z M[H2SO4] z[H2SO4] 4 No Yes No No

1 Fe+H2SO4 Fixed volume 5.0 mL 1.0 g/mL 1.0 25.0°C

Water 1 10.0 mL Current position

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A 004 Stir Speed Duration 005 Titration (EQP) Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Wait time Control Control Titrant addition dE(set) dV(min) dV(max) Meas. val. acquisition dE dt t(min) t(max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number EQPs Combined termination criteria 006 Calculation R1 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 35% 10 s

Rondo60/1A Conditioning beaker 10 s 35%

HCl 0.1 mol/L pH DGi111-SC pH No 35% Volume 1.0 mL 10 s User Dynamic 8.0 0.02 mL 0.2 mL Equilibrium controlled 0.5 mV 1.0 s 3.0 s 30.0 s Standard 3.0 pH/mL Negative No No 10.0 mL No No Yes 1 No

No Per sample Per sample Last titration function No No Last titration function No No No No No No No No No No No No

012 Record Summary Results Raw results Ressource data Calibration curve Method Series data

Yes Yes No No No No No

Total sum mol/L R=(H[H3]-Q)*C/m C=1 M[H2SO4] z[H2SO4] 4 No No No No

METTLER TOLEDO

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Titration Application M060-2010

METTLER TOLEDO

Application M463-2010

Determination of Cr(III) by Back Titration in an Electroplating Bath
Chromium (III) is determined by back titration of excess cerium(IV) sulphate solution with sodium nitrite.

Sample

2 mL aliquot of chromium(III) bath (approx. 8 g/L Cr(III))

Preparation and Procedures
CAUTION: Work in a fume hood. Use gloves, lab coat and safety goggles. Principle: Cr(III) is determined as Cr2O3 by back titration of excess cerium(IV) sulphate , Ce(SO4)2, solution.

Compound

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

Chemicals

- Deionized water - Nitric acid 1:1 - Cerium(IV) sulphate , Ce(SO4)2, c(Ce(SO4)2) = 0.1 mol/L Sodium nitrite, NaNO2 c(1/2 NaNO2) = 0.2 mol/L

Back value determination: 1.) 2.) 3.) Fill up a titration beaker with 50 mL with deionized water. 1:1 diluted HNO3 and Ce(SO4)2 solution are added with two dosing units. Ce(IV) is titrated with sodium nitrite. The back value is stored as B[Back] in mmol

Titrant

Sample titration:

Standard

Cerium(IV) sulphate , Ce(SO4)2

1.)

Pipette 2 mL of chromium(III) bath to a beaker and fill up to 50 mL with deionized water. Sample preparation is automated by adding 1:1 diluted HNO3 and excess Ce(SO4)2 with two dosing units. Cr(III) is oxidized by excess Ce(IV) to Cr(VI) by the following reaction: 3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+

Indication

DMi140-SC

2.)

Chemistry

Cr(III) oxidation by Ce(IV): 3 Ce4+ + Cr3+ → 3 Ce3+ + Cr6+ Back titration of Ce4+: 2 Ce4+ + NO2- + H2O → 2 Ce3- + NO3- + 2 H+

3.)

4.)

Cr(III) is then determined by back titration of unreacted Ce(IV) using sodium nitrite (NaNO2): 2 Ce4+ + NO2- + H2O → 2 Ce3- + NO3- + 2 H+

Calculation

Cr2O3 content in g/L: R=(B[Blank]-Q)*C/m; C = M/(z*2) (2 x Cr in Cr2O3) B[Back] = Back value in mmol Ce(SO4)2

Remarks
- It is not necessary to heat the sample as mentioned in older applications. - The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample. - Rinse the electrode after each sample. If necessary, clean the metal ring of the electrode with a paper tissue at the end of each sample series.

Waste disposal

Heavy metal waste

Author, Version
METTLER TOLEDO

Susanne Wahlen, MSG Anachem, April 2010

Page 1 of 4

Titration Application M463-2010

Instruments

- T50/70/90 Titration Excellence - XS205 Balance - Rondo 20 Sample Changer 2 x 10 mL DV1010 burette 1 x 5 mL DV1005 burette 2 x additional dosing unit Titration beakers ME-101974 LabX titration pro

Accessories

Results
METTLER TOLEDO T90 Method: 002 Results Series start time No. 1/6 Note / ID Cr2O3 CHROM(III) 16.04.2010 17:08:37 Start time 16.04.2010 17:08:33 Rx R1 = R2 = 2/6 Cr2O3 16.04.2010 17:20:33 R1 = R2 = 3/6 Cr2O3 16.04.2010 17:32:48 R1 = R2 = 4/6 Cr2O3 16.04.2010 17:45:02 R1 = R2 = 5/6 Cr2O3 16.04.2010 17:57:14 R1 = R2 = 6/6 Cr2O3 16.04.2010 18:09:31 R1 = R2 = Result 2.018 Unit mL Name Consumption Chromium(III)oxide Consumption Chromium(III)oxide Consumption Chromium(III)oxide Consumption Chromium(III)oxide Consumption Chromium(III)oxide Consumption Chromium(III)oxide 16.04.2010 17:07:54

7.314 (2) g/L 2.037 7.265 2.048 7.237 2.055 7.221 2.044 7.247 2.052 7.228 mL g/L mL g/L mL g/L mL g/L mL g/L

Statistics:
(2) excluded

n = 5

R2 = 7.240 ± 0.018 g/L

s = 0.0172

srel: 0.238%

Titration curve

Sample 2/6

METTLER TOLEDO

Page 2 of 4

Titration Application M463-2010

Table of measured values
Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s -------------------------------------------------------------------------------------------0 1291.3 0 0.02 0.02 1290.7 -0.6 3 0.04 0.02 1290.2 -0.5 6 0.09 0.05 1289 -1.2 9 0.215 0.125 1286.2 -2.8 12 0.415 0.2 1281.4 -4.8 -23.91 15 0.615 0.2 1276.3 -5.1 -25.16 18 0.815 0.2 1271 -5.3 -27.73 21 1.015 0.2 1264.8 -6.2 -32.32 24 1.215 0.2 1257.7 -7.1 -40.05 28 1.415 0.2 1249 -8.7 -53.77 32 1.583 0.168 1239.7 -9.3 -75.21 36 1.696 0.113 1231.5 -8.2 -101.42 41 1.7815 0.0855 1223.4 -8.1 -136.73 46 1.8455 0.064 1215.2 -8.2 -188.09 51 1.8915 0.046 1207.4 -7.8 -280.21 58 1.9275 0.036 1199.4 -8 -475.65 65 1.955 0.0275 1190.8 -8.6 -755.81 73 1.975 0.02 1182.4 -8.4 -917.64 83 1.995 0.02 1170.1 -12.3 -1512.53 96 2.015 0.02 1144.1 -26 -1876.36 125 2.035 0.02 1086 -58.1 -1570.8 155 EQP1 2.036912 1077.8 -1935.31 2.055 0.02 999.7 -86.3 -1302.36 185 2.075 0.02 982.9 -16.8 -1232.25 200 2.124 0.049 965.5 -17.4 -829.18 211 2.177 0.053 954.6 -10.9 220 2.2445 0.0675 945.6 -9 226 2.3375 0.093 936.9 -8.7 233 2.4595 0.122 929.1 -7.8 239 2.6405 0.181 921 -8.1 244

Comments --

METTLER TOLEDO

Page 3 of 4

Titration Application M463-2010

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume [mL] Density [g/mL] Correction factor Temperature General titration T50 / T70 / T90 002 CHROM(III) Administrator 13.04.2010 14:45:58 16.04.2010 17:07:54 admin No None Accompanying stating Accompanying stating Condition Condition 009 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 010 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 011 Record Summary Results Raw results Table of meas. values Sample data Resource data E - V dE/dV - V log dE/dV - V d2E/dV2 - V BETA – V E - t V - t dV/dt - t T – t E – V & dE/dV – V V – t & dV/dt – t Method Series data Condition 012 End of sample No 30 None 0 User Dynamic 8.0 0.02 0.2 Equilibrium controlled 0.5 1.0 3.0 30 Standard 200.0 Negative 0 No 20 No No Yes 1 No No No

1 Cr2O3 Fixed volume 2.0 1.0 1.0 25.0

Consumption mL R1=VEQ 1 M[none] z[None] 3 No Yes No No No

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A LidHandling No 004 Stir Speed [%] Duration [s] Condition 005 Dispense (normal) [1] Titrant Concentration [mol/L] Volume [mL] Dosing rate [mL/min] Condition 006 Dispense (normal) [2] Titrant Concentration [mol/L] Volume [mL] Dosing rate [mL/min] Condition 007 Stir Speed [%] Duration [s] Condition 008 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Waiting time [s] Control Control Titrant addition dE (set value) [mV] dV (min) [mL] dV (max) [mL] Mode dE [mV] dt [s] t(min) [s] t(max) [s] Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria 30 2 No

Chromium(III)oxide g/L R2=(B[Back]-Q)*C/m M/(z*2) M[Cr2O3] z[Cr2O3] 3 No Yes No No No

HNO3 (1 :1) 1 5.0 60.0 no Ce(SO4)2 0.1 10.0 60.0 no 30 300 No

½ NaNO2 0.2 mV DMi140-SC mV

No Per sample Per sample Last titration function No No Last titration function Last titration function No No No No No No No No No No No No

METTLER TOLEDO

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Titration Application M463-2010

METTLER TOLEDO

Application M464-2010

Iodometric Titration of Cr(VI) in an Electroplating Bath
Chromium is determined by redox titration of free iodine generated by reduction of Cr(VI) to Cr(III) with potassium iodide. Iodine is titrated with sodium thiosulfate and a combined platinum ring sensor. 5 mL aliquot from 1:100 diluted chromium(VI) bath

Sample

Preparation and Procedures
CAUTION: Work in a fume hood. Use gloves, lab coat and safety goggles. Sample titration: -

Compound

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

Chemicals

- Deionized water - Sulphuric acid, 1:1 - Potassium iodide solution, KI 10% KI Sodium thiosulphate, Na2S2O3 c(Na2S2O3)=0.1 mol/L

2.5 mL chromium bath is diluted with deionized water to 250 mL. 5 mL of diluted aliquot corresponds to 0.05 mL of original sample. The latter value is defined as fixed sample volume. Sulphuric acid is automatically added by a dosing unit. The addition of potassium iodide KI by a pump leads to the reduction of Cr(VI) to Cr(III) according to the following reaction: 2 Cr6+ + 6I- = 2 Cr3+ + 3 I2 (z = 3) The amount of iodine formed is proportional to the Cr(VI) content. Generated I2 is then titrated with Na2S2O3: 2 S2O32- + I2 = S4O62- + 2 I-

-

Titrant

-

Standard

Potassium iodate, KIO3 -

Indication

DMi140-SC

Note: Stir moderately. Vigorous stirring causes loss of I2.

Chemistry

Cr(VI) reduction to Cr(III): 2 Cr6+ + 6I- → 2 Cr3+ + 3 I2 Titration of iodine: 2 S2O32+ + I2 → S4O62- + 2 I-

Remarks
- 1 mL Na2S2O3 corresponds to 3.33 mg CrO3. - The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample. - Rinse the electrode after each sample. - If necessary, clean the metal ring of the sensor with a paper tissue at the end of each sample series.

Calculation

CrO3 content in g/L: R=Q*C/m C=M/z

Waste disposal

Heavy metal waste

Author, Version
METTLER TOLEDO

Susanne Wahlen, MSG Anachem, April 2010
Page 1 of 4 Titration Application M464-2010

Instruments

-

T50/70/90 Titration Excellence XS205 Balance Rondo 20 Sample Changer SP250 Peristaltic pump ME-51108016 2 x 10 mL DV1010 burette 1 x additional burette drive Titration beakers ME-101974 LabX titration pro

Accessories

Results
METTLER TOLEDO T90 DL90 Fumehood Method: 001 Results Series start time No. Note / ID 1/8 CrO3 2/8 3/8 4/8 5/8 6/8 7/8 8/8 CrO3 CrO3 CrO3 CrO3 CrO3 CrO3 CrO3

CHROMIUM(VI) 15.04.2010 16:06:37 Start time 15.04.2010 16:06:38 15.04.2010 16:13:56 15.04.2010 16:21:11 15.04.2010 16:28:28 15.04.2010 16:35:46 15.04.2010 16:43:11 15.04.2010 16:50:20 15.04.2010 16:57:35

15.04.2010 17:06:09

Rx R1 R2 R1 R2 R1 R2 R1 R2 R1 R2 R1 R2 R1 R2 R1 R2

= = = = = = = = = = = = = = = =

Result 4.381 292.065 4.381 292.051 4.428 295.143 4.432 295.412 4.532 302.104 (2) 4.269 284.538 (2) 4.368 291.178 4.357 290.468

Unit mL g/L mL g/L mL g/L mL g/L mL g/L mL g/L mL g/L mL %

Name Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide Consumption Chromium(VI)oxide srel: 0.707%

Statistics:
(2) excluded

n = 6

R2 = 292.719 ± 2.071 g/L

s = 2.071

Titration curve

Sample 2/8

METTLER TOLEDO

Page 2 of 4

Titration Application M464-2010

Table of measured values
Volume Increment Signal Change 1st deriv. Time mL mL mV mV mV/mL min:s -------------------------------------------------------------------------------------------0 NaN 355.9 NaN NaN 0 2 2 346.5 -9.4 NaN 6 2.05 0.05 346.4 -0.1 NaN 9 2.1 0.05 346.1 -0.3 NaN 12 2.15 0.05 345.8 -0.3 NaN 15 2.2 0.05 345.5 -0.3 -5.91 18 2.25 0.05 345.2 -0.3 -6.63 22 2.3 0.05 344.9 -0.3 -6.6 25 2.35 0.05 344.5 -0.4 -6.8 28 2.4 0.05 344.2 -0.3 -7 31

. . .
3.1 4 4.05 4.1 4.15 4.2 4.25 4.3 4.35 4.4 4.431621 4.45 4.5 4.55 4.6 4.65 4.7 4.75 4.8 4.85 4.9

. . .
0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 NaN 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05 0.05

. . .
338.3 323 321.4 319.5 317.2 314.5 311.2 306.7 300.2 285.7 233.7 203.5 178.9 168.9 163 158.7 155.9 153.2 150.8 148.7 146.8

. . .
-0.5 -1.5 -1.6 -1.9 -2.3 -2.7 -3.3 -4.5 -6.5 -14.5 NaN -82.2 -24.6 -10 -5.9 -4.3 -2.8 -2.7 -2.4 -2.1 -1.9

. . .
-10.28 -30.8 -34.63 -39.51 -40.39 22.69 -78.76 -286.78 -501.86 -643.36 -667.44 -665.73 -560.11 -360.3 -138.14 2.37 NaN NaN NaN NaN NaN

. . .
73 128 131 134 137 140 144 147 150 154 NaN 164 175 182 188 192 195 198 202 204 208

EQP1

Comments --

METTLER TOLEDO

Page 3 of 4

Titration Application M464-2010

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume [mL] Density [g/mL] Correction factor Temperature General titration T50 / T70 / T90 001 Chromium(VI) Administrator 13.04.2010 10:32:13 23.04.2010 12:23:15 admin No None 009 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition Consumption mL R1=VEQ 1 M[none] z[None] 3 No Yes No No No

1 CrO3 Fixed volume 0.05 1.0 1.0 25.0

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo20/1A Lid Handling No 004 Dispense (normal) [1] Titrant Concentration Volume [mL] Dosing rate [mL/min] Condition 005 Pump Auxiliary reagent Volume [mL] Condition 006 Pump Auxiliary reagent Volume [mL] Condition 007 Stir Speed [%] Duration [s] Condition 008 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Volume [mL] Waiting time [s] Control Control Titrant addition dV [mL] Mode dE [mV] dt [s] t(min) [s] t(max) [s] Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria 30 90 No KI 5.0 No Water 40.0 no

H2SO4 1:1 4.6 5.0 60.0 no

010 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 011 Rinse Auxiliary reagent Rinse cycles Vol. per cycle [mL] Position Drain Condition 012 End of sample 013 Park Titration stand Position Condition

Chromium(VI)oxide g/L R2=Q*C/m M/z M[Chromium(VI)oxide] z[Chromium(VI)oxide] 3 No Yes No No No

Water 1 10 Current position No No

Rondo20/1A Rinse beaker No

Na2S2O3 0.1 mol/L mV DMi140-SC mV No 30 Volume 2.0 0 User Incremental 0.05 Equilibrium controlled 1.0 2.0 3.0 10.0 Standard 200.0 Negative 0 No 10 No No Yes 1 No

METTLER TOLEDO

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Titration Application M464-2010

METTLER TOLEDO
Determination of Manganese in Manganese Ores

Application M461-2010

Manganese is determined in slighlty acidic-neutral digested solutions by redox titration at 80°C with potassium permanganate KMnO4 as a titrant. The potential change is monitored by a combined platinum ring electrode.

Sample

Manganese (IV) dioxide acid digested solution, MnO2 (approx. 0.5 g/500 mL) 5 mL Manganese, MnO2 M = 86.94; z = 2

Preparation and Procedures
CAUTION: Work in a fume hood, use safety goggles and wear gloves. Note: Check under “Comments and method” for the dissolution of manganese ores Sample preparation with pure MnO2:

Compound

Chemicals

32% hydrochloric acid, HCl 10% zinc oxide suspension, (ZnO in water) ZnSO4 (10g/200 mL H2O) Deionized water

Titrant

Potassium permanganate, KMnO4 c(1/3 KMnO4) = 0.06 mol/L Sodium oxalate, Na2C2O4 (for 1/5 KMnO4), 0.025-0.040 g Combined redox Pt-electrode e.g. DMi140-SC
Digestion and reduction to Mn(II): MnO2 + 4 HCl → MnCl2 + Cl2 + 2 H2O Titration from Mn(II) to Mn(IV): 3 Mn2+ + 2 MnO4 + 2 ZnO 2+ 5 MnO2 + 2 Zn →

- Approximately 0.5 g pure (> 99.9%) MnO2 is accurately weighed into a glass titration beaker. - 20 mL deionized water HCl is added. - 30 mL 32% concentrated HCl is added. - The sample is heated (70-90°C) on a hot plate under stirring to dissolve manganese dioxide. - After complete dissolution, the solution is cooled to room temperature and is added into a 500 mL volumetric flask. - Add deionized water to approx. 450 mL, gently shake the solution. If necessary, neutralize with Na2CO3 up to a neutral or slightly acidic solution. - Fill up to the mark with deionized water. Titration of Mn(II): - 5 mL of the digested solution is added into a glass titration beaker. - Add 60 mL deionized water. - Add 3 mL 10% ZnO suspension, and 5 mL ZnSO4. - Start immediately the titration with KMnO4.

Standard Indication

Chemistry

Remarks
- The content determination is based on a comparative titration of a standard solution. Thus, two titrations are performed: 1) Calibration titration with std. solution of known concentration, where a factor in mg/mL MnO2 is determined. 2) Content determination - Perform both the calibration and sample titrations under exactly the same conditions. - In this application, pure manganese dioxide has been used to prepare a digested ore sample. - The parameters have been optimized for this application. It may be necessary to adapt the method to your sample.
Titration Application M461-2010

Auxiliary reaction (masking of iron): 2 Fe3+ + 3 ZnO + 3 H2O → 2 Fe(OH)3 + 3 Zn2+

Calculation

Content (%, as Mn): R1 = Q*C/m C = M/(10*z) Neutralize with sodium hydroxide before final disposal as metal solution. Cosimo De Caro, MSG Anachem, April 2010

Waste disposal Author, Version
METTLER TOLEDO

Page 1 of 8

Instruments

-

T50/T70/T90 Titration Excellence XS205 Balance DH100 heating system Rondo 20 sample changer

Accessories

- 1 x 10 mL DV1010 burette - Glass titration beaker ME-101446 - LabX pro titration software

Calibration factor: Results
Sample Factor (mg/mL) 2.863 2.988 2.866 2.743 2.950 3.015 2.980 3.016 ± ± ± ± ± ± ± ± 0.067 0.052 0.018 0.025 0.041 0.024 0.024 0.063 n srel (%) 6 6 6 6 6 6 6 6 2.345 1.726 0.626 0.924 1.381 0.802 0.812 1.095 ZnO H2O mL mL 3 3 3 3 3 3 3 20 10 10 5 5 5 3 3 60 60 60 60 60 60 60 40 50 60 60 60 60 60 60 Parameters INC TFIX mL s 0.1 0.1 0.1 0.1 0.1 0.05 0.1 0.1 30 15 30 15 30 30 15 45 80°C 80°C 80°C 60°C 80°C 80°C 80°C 80°C manual manual Rondo20 Rondo20
Rondo20, 0.7 mL predisp. Rondo20, 1 mL predisp. Rondo20 12 days later

Acid digested MnO2 solution, 5 mL (5.118 mg MnO2)

Rondo20

Acid digested MnO2 solution, 5 mL (5.368 mg MnO2) Standard solution MnSO4 x H2O in H2O 5 mL
(9.576 mg MnSO4 x H2O)

3.010 ± 0.030 3.041 ± 0.058 2.997 ± 0.048 7.242 ± 0.184 6.446 ± 0.144 5.709 ± 0.213 5.690 ± 0.142

6 0.999 4 1.905 4 1.600 5 2.545 6 2.242 5 3.724 5 2.504

0.1 30 0.1 30

80°C Rondo20 80°C Rondo20

0.02-1 mL, EQU: 0.5/3 mV/s, t=15-45 s

0.1 30 80°C Rondo20 No acid 0.1 30 80°C Rondo20 1 mL 0.5 M HCl 0.1 30 80°C Rondo20 1 mL 0.5 M HCl 5 mL ZnSO4 (10g/200 mL H2O) 0.1 30 80°C Rondo20 1 mL 0.5 M HCl 5 mL ZnSO4 (10g/200 mL H2O) Conditioning: 0.5 M HCl 0.1 5 80°C Rondo20 10 mL ZnSO4 (10g/200 mL H2O Conditioning: H2O 0.1 5 80°C Rondo20 3 mL ZnSO4 (10g/200 mL H2O) Conditioning: H2O 0.1 5 80°C Rondo20 5 mL ZnSO4 (10g/200 mL H2O) Conditioning: H2O

5.689 ± 0.087

3 1.535

5

50

5.994 ± 0.141

3 2.357

1

60

6.019 ± 0.039

3 0.654

3

60

Note: When using less than 3 mL ZnO suspension no titration was possible. With more than 3 mL, the result is more or less constant. A variation of several parameters such as the titration method parameters (increments, titration modes, signal acquisition,..) and sample preparation (use of Mg standard solution, pH neutral sample solution,…) did not show any significant influence on the results.

METTLER TOLEDO

Page 2 of 8

Titration Application M461-2010

Calibration factor: Titration curve

Sample 1/6 - 8.4.2010 09:02 CDCMnOMnO2RONDO

Calibration factor: Table of measured values
Volume Increment Signal Change 1st deriv. Time Temperature mL mL mV mV mV/mL s °C -------------------------------------------------------------------------------------0.0000 NaN 393.7 NaN NaN 0 25.0 0.1000 0.1000 407.0 13.3 NaN 30 25.0 0.2000 0.1000 415.5 8.5 NaN 60 25.0 0.3000 0.1000 418.6 3.1 NaN 90 25.0 0.4000 0.1000 425.4 6.8 NaN 121 25.0 0.5000 0.1000 430.0 4.6 44.67 151 25.0 0.6000 0.1000 434.2 4.2 51.44 181 25.0 0.7000 0.1000 440.1 5.9 55.84 211 25.0 0.8000 0.1000 448.4 8.3 54.58 241 25.0 0.9000 0.1000 447.6 -0.8 57.50 272 25.0 1.0000 0.1000 459.9 12.3 52.96 302 25.0 1.1000 0.1000 462.2 2.3 46.86 332 25.0 1.2000 0.1000 467.1 4.9 39.99 362 25.0 1.3000 0.1000 473.4 6.3 29.44 392 25.0 1.4000 0.1000 476.0 2.6 69.54 422 25.0 1.5000 0.1000 484.9 8.9 165.42 452 25.0 1.6000 0.1000 497.0 12.1 275.11 483 25.0 1.7000 0.1000 523.3 26.3 350.54 513 25.0 EQP1 1.764479 NaN 562.9 NaN 365.64 NaN NaN 1.8000 0.1000 584.7 61.4 363.09 543 25.0 1.9000 0.1000 620.4 35.7 303.67 573 25.0 2.0000 0.1000 644.0 23.6 191.62 603 25.0 2.1000 0.1000 644.3 0.3 57.39 634 25.0 2.2000 0.1000 644.7 0.4 -50.26 664 25.0 2.3000 0.1000 640.6 -4.1 NaN 694 25.0 2.4000 0.1000 630.8 -9.8 NaN 724 25.0 2.5000 0.1000 619.4 -11.4 NaN 754 25.0 2.6000 0.1000 609.0 -10.4 NaN 784 25.0 2.7000 0.1000 605.8 -3.2 NaN 815 25.0
Sample 1/6 - 8.4.2010 09:02 CDCMnOMnO2RONDO

METTLER TOLEDO

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Titration Application M461-2010

Sample determination: Results
Calibration factor: Sample Factor
(mg/mL)

n

srel (%) 2.345 0.626 1.381 1.707

ZnO H2O mL mL 3 3 3 60 60 60

Parameters INC TFIX mL s 0.1 30 0.1 30 0.1 30 80°C manual 80°C Rondo20 80°C
Rondo20, 0.7 mL predisp.

Acid digested MnO2 solution, 5 mL (5.118 mg MnO2)

2.863 ± 0.067 2.866 ± 0.018 2.950 ± 0.041

6 6 6 3

Average calibration factor

2.893 ± 0.049

Sample determination: Sample Consumption (mL)
Recovery rate (%)

ZnO H2O mL mL

Parameters INC TFIX mL s

Acid digested MnO2 solution, 5 mL (5.118 mg MnO2)
Sample Series (9) 24.03.2010 12:25

1/6 2/6 3/6 4/6 5/6 6/6 Average (%) Std. deviation (%) Rel. Std. dev. (%)

1.774 1.774 1.781 1.799 1.798 1.787

100.28 100.28 100.67 101.69 101.63 101.01 100.93 0.630 0.624

3 3 3 3 3 3

60 60 60 60 60 60

0.1 0.1 0.1 0.1 0.1 0.1

30 30 30 30 30 30

80°C 80°C 80°C 80°C 80°C 80°C

Rondo20 Rondo20 Rondo20 Rondo20 Rondo20 Rondo20

Sample Series (8) 25.03.2010 09:19

1/6 2/6 3/6 4/6 5/6 6/6 Average (%) Std. deviation (%) Rel. Std. dev. (%)

1.706 1.731 1.778 1.723 1.741 1.733

96.43 97.85 100.50 97.39 98.41 97.96 98.09 1.359 1.385

3 3 3 3 3 3

60 60 60 60 60 60

0.1 0.1 0.1 0.1 0.1 0.1

30 30 30 30 30 30

80°C 80°C 80°C 80°C 80°C 80°C

Rondo20, 0.7 mL predispensing Rondo20, 0.7 mL predispensing Rondo20, 0.7 mL predispensing Rondo20, 0.7 mL predispensing Rondo20, 0.7 mL predispensing Rondo20, 0.7 mL predispensing

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Titration Application M461-2010

Sample determination: Titration curve

Sample 6/6 – 24.3.2010 12:25 CDCMnOMnO2RONDO2 (9)

Sample determination: Table of measured values
Volume Increment Signal Change 1st deriv. Time Temperature mL mL mV mV mV/mL s °C -------------------------------------------------------------------------------------0.0000 NaN 430.6 NaN NaN 0 25.0 0.1000 0.1000 429.7 -0.9 NaN 30 25.0 0.2000 0.1000 428.5 -1.2 NaN 60 25.0 0.3000 0.1000 430.5 2.0 NaN 91 25.0 0.4000 0.1000 431.2 0.7 NaN 121 25.0 0.5000 0.1000 431.4 0.2 7.83 151 25.0 0.6000 0.1000 430.7 -0.7 6.44 181 25.0 0.7000 0.1000 433.3 2.6 6.78 211 25.0 0.8000 0.1000 433.7 0.4 10.33 242 25.0 0.9000 0.1000 434.4 0.7 12.53 272 25.0 1.0000 0.1000 435.2 0.8 14.11 302 25.0 1.1000 0.1000 438.2 3.0 17.03 332 25.0 1.2000 0.1000 439.5 1.3 21.44 362 25.0 1.3000 0.1000 441.6 2.1 -21.34 392 25.0 1.4000 0.1000 445.0 3.4 -0.37 423 25.0 1.5000 0.1000 449.4 4.4 140.21 453 25.0 1.60000 0.1000 453.6 4.2 298.77 483 25.0 1.7000 0.1000 462.4 8.8 410.61 513 25.0 EQP1 1.787293 NaN 542.9 NaN 445.71 NaN NaN 1.8000 0.1000 554.6 92.2 445.67 543 25.0 1.9000 0.1000 626.3 71.7 393.96 574 25.0 2.0000 0.1000 626.4 0.1 268.65 604 25.0 2.1000 0.1000 632.8 6.4 112.76 634 25.0 2.2000 0.1000 640.2 7.4 -0.71 664 25.0 2.3000 0.1000 644.8 4.6 NaN 694 25.0 2.4000 0.1000 647.9 3.1 NaN 724 25.0 2.5000 0.1000 652.2 4.3 NaN 754 25.0 2.6000 0.1000 656.2 4.0 NaN 785 25.0 2.7000 0.1000 657.0 0.8 NaN 815 25.0
Sample 6/6 – 24.3.2010 12:25 CDCMnOMnO2RONDO2 (9)

METTLER TOLEDO

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Titration Application M461-2010

Comments and Methods
• A direct titration always leads to lower content values (see below). Thus, the determination of manganese in ores is based on a comparative titration between a standard and the sample solution: 1. First, the titrant consumption for the titration of a standard solution of known concentration is determined. The result is stored as auxiliary value H[CalibFactorMn] in mg/mL MnO2. A known amount of MnO2 is digested in acid in order to get Mn(II)-ions into solution. 2. Subsequently, the titrant consumption for the sample is determined. The result is obtained by multiplying the calibration factor H[CalibFactorMn] with the titrant consumption. • • Only a slight excess of ZnO suspension is needed. It is very important that both titrations are performed exactly in the same way i.e. stirring speed, T,…

Manganese ore dissolution: In this application, the titration has been performed using acid digested solution of MnO. The application can be also run with manganese ores. A customer procedure for the dissolution of manganese ores is as it follows:
Weigh 0.1 g of dried sample in a platinum crucible and 2 g of Na2CO3; Leave the crucible in a muffle oven at 700°C, raise the temperature until 950°C and leave it during 20min; Remove the sample and wait until the sample is cooled down; Dissolve the molten mass in a 250 mL beaker with 50mL 1:1 HCl on a hot plate at 100°C and shake; Transfer to an 1000mL Erlenmeyer flask and leave on a hot plate at 250°C until the volume is reduced to 10mL. Subsequently, leave it on the hot plate at 100°C until dryness; - Add 700 mL of hot water and leave to boil on the hot plate; - Add sufficient 10% (w/w) ZnO suspension until the solution turns white, and titrate in the heat with KMnO4 to EQP.

Chemical reaction: Mn(II) is titrated by permanganate titration at 80°C in a neutral or slightly acidic solution leading to the formation of Mn(IV) according to the reaction 3 Mn2+ + 2 MnO4- + 2 ZnO → 5 MnO2 + 2 Zn2+

In iron-manganese ores or in manganese alloys, iron needs to be masked since it affects the manganese determination. This is done by precipitating iron with zinc oxide. 2 Fe3+ + 3 ZnO + 3 H2O → 2 Fe(OH)3 + 3 Zn2+

A detailed analysis of the chemical reaction shows that Mn(IV) is precipitated as manganese oxyde hydrate, MnO2·H2O, a dark brown compound which is clearly visible in the solution: 2 MnO4+ 3 Mn2+ + 7 H2O → 5 MnO2·H2O + 4 H+

The formation of manganese oxyde hydrate leads to adsorption of bivalent ions such as Mn(II) and Zn(II). If unreacted Mn(II) is adsorbed, then mixed Mn(II)-Mn(IV) oxide hydrate with formula Mn(HMnO3)2 is precipitated. As a consequence, the titrant consumption is smaller than expected. To avoid it, ZnO suspension and also ZnSO4 solution are added. Thus, the addition of excess ZnO suspension is needed to first neutralize the resulting acid protons, to mask iron, and also to suppress adsorption and co-precipitation of unreacted Mn(II). Nevertheless, the oxidation of Mn(II) to Mn(IV) seems still not to be complete when reaching the equivalence point. Thus, it is necessary to heat again to 80°C the titrated solution, then continues the analysis until the equivalence point is reached again. For this reason, a comparative titration is more suitable for routine analysis. Literature:
[1] [2] [2] [4] www.chemguide.co.uk/inorganic/transition/manganese.html, and www.titrations.info/permanganate-titration . Jander Jahr, “Massanalyse”, ed. by Gerhard Schulze and Jürgen Simon, 14th Edition, de Gruyter, 1986 (German). Othmar G. Koch, „Analytische Chemie des mangans“, Springer-Verlag, 1985 (German). József Mika, „Metallurgische Analysen”, Akademische Verlagsgesellschaft, Geest & Portig K.-G., Leipzig 1964 (German).

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Titration Application M461-2010

Calibration factor
001 Title Type Compatible with ID Title Author Date/Time Modified Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume Density Correction factor Temperature General titration T50 / T70 / T90 m461Calib Calibration factor Mn METTLER TOLEDO 01.06.2010 15:00:00 --No None

008 Auxiliary instrument Control type Name Mode Time 009 Calculation R1 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 010 Calculation R2 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 011 Rinse Titration stand Auxiliary reagent Rinse cycles Vol.per cycle Position Drain 012 Conditioning Titration stand Type Interval Position Time Speed 013 End of sample

Out TTL (Single pin) DH100 TTL off Fixed time 2 s

1 MnO2 Standard solution Fixed volume 5.0 mL 1.0 g/mL 1.0 25.0°C

Consumption mL R=VEQ C=1 M[None] z[None] 3 No Yes No No

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A 004 Stir Speed Duration 005 Auxiliary instrument Control type Name Mode Time 50% 60 s

Calibration factor mg/mL R2=(C*m)/VEQ C=H[MnO2Std] M[None] z[None] 3 No No No No

Out TTL (Single pin) DH100 TTL on Fixed time 2 s

006 Measure (normal) [1] Sensor Type Temperature Sensor DT1000 Unit °C Stir Speed 50% Acquisition of measured values Acquisition Set value Mode T>set value Set value 80°C t(max) 300 Mean value No 007 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Wait time Control Control Titrant addition dV Meas. val. acquisition dt Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number EQPs Combined termination criteria

Rondo60/1A Water 1 20 Current position No

Rondo60/1A Fix 1 Conditioning beaker 60 s 70%

1/3 KMnO4 0.06 mol/L mV DMi140-SC mV No 50% None 0 s User Incremental 0.1 mL Fixed time 30 s Standard 150 mV/mL Positive 0 No 10.0 mL No No Yes 1 No

014 Auxiliary value Name Formula H=

CalibFactor Mean[R2]

--------------------------------------------------------------

Calculation R2: C: H[MnO2Std] Concentration of the digested MnO2 standard solution e.g. 0.5118 g MnO2 in 500 mL H = 0.5118/500 = 0.0010236 g/mL = 1.0236 mg/mL

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Titration Application M461-2010

Sample titration
001 Title Type Compatible with ID Title Author Date/Time Modified Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume Density Correction factor Temperature General titration T50 / T70 / T90 m461sample Sample titration Mn METTLER TOLEDO 01.06.2010 15:00:00 --No None

Mode Time 009 Calculation R1 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 010 Calculation R2 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 011 Calculation R3 Result Result unit Formula Constant M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer 012 Rinse Titration stand Auxiliary reagent Rinse cycles Vol.per cycle Position Drain 013 Conditioning Titration stand Type Interval Position Time Speed 014 End of sample 50% None 0 s User Incremental 0.1 mL Fixed time 30 s Standard 150 mV/mL Positive 0 No 10.0 mL No No Yes 1 No

Fixed time 2 s

Consumption mL R=VEQ C=1 M[None] z[None] 3 No Yes No No

1 Digested ore solution Fixed volume 5.0 mL 1.0 g/mL 1.0 25.0°C

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A 004 Stir Speed Duration 005 Auxiliary instrument Control type Name Mode Time 50% 60 s

MnO2 Amount mg R2=H[CalibFactor]*VEQ C=1 M[None] z[None] 3 No No No No

Out TTL (Single pin) DH100 TTL on Fixed time 2 s

006 Measure (normal) [1] Sensor Type Temperature Sensor DT1000 Unit °C Stir Speed 50% Acquisition of measured values Acquisition Set value Mode T>set value Set value 80°C t(max) 300 Mean value No 007 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Wait time Control Control Titrant addition dV Meas. val. acquisition dt Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number EQPs Combined termination criteria 008 Auxiliary instrument Control type Name

MnO2 Content % R3=((R2/1000)/H[Ore])*100 C=H[Ore] M[MnO2] z[MnO2] 3 No No No No

Rondo60/1A Water 1 20 Current position No

1/3 KMnO4 0.06 mol/L mV DMi140-SC mV No

Rondo60/1A Fix 1 Conditioning beaker 60 s 70%

Out TTL (Single pin) DH100 TTL off

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Titration Application M461-2010

METTLER TOLEDO

Application M466A-2010

Aluminum Content in Aluminum Ore (Bauxite) – Bayer Liquor
Determination of free alkali and aluminum content in aluminum ore (Bauxite) by potentiometric titration with hydrochloric acid according to the Bayer procedure. The titration is monitored with a pH glass combined sensor.

Sample

5 mL alkaline digestion solution from original aluminum ore (Bayer Liquor, 30.23 g/500 mL) Aluminum trihydroxide, Al(OH)3 M = 78.00 g/mol, z = 3 Sodium hydroxide, NaOH M = 40.00 g/mol, z = 1 25% Na-gluconate, NaC6H11O7 30% Potassium fluoride, KF Deionized water (see Preparation and

Preparation and Procedures
CAUTION: Work in a fume hood and wear gloves and safety goggles. Weight in about 30 gr into a 600 mL Erlenmeyer flask. Add 350 mL 7 mol/L NaOH and cover it with a watch glass. Heat the sample on a heating plate set at 200°C, and keep it boiling while continuously stirring for at least 4 hours. The alumina is first converted into aluminum hydroxide, Al(OH)3, and further to [Al(OH)4]which is dissolved in the hydroxide solution. Some components are not dissolved; these are mainly insoluble iron hydroxide compounds. Let the solution cool down; prepare a 500 ml volumetric flask with a glass funnel and a paper filter to avoid the solid impurities. Filter the cooled solution into the 500 mL volumetric flask. Wash the paper filter with 100 mL 7 M NaOH. Mix well and fill up to the mark with deionized water, and mix again. Note: Temperature can increase again; thus, filling with water may be necessary again. 5 mL sample solution is added to a titration beaker together with 35 mL deion. water.

Compound

Chemicals

Titrant

Hydrochloric acid, HCl c(HCl) = 1 mol/L c(HCl) = 0.1 mol/L

-

-

Standard

Tris(hydroxymethyl)aminomethane, THAM DGi115-SC

Indication

-

Chemistry

OH- + H3O+ → 2 H2O see “Comments” for more detailed information

-

-

Calculation

Free Caustic NaOH (g/L): R1 = (Q-Q2)*C/m ; C=M/z Free Carbonate CaCO3 (g/L): R2 = Q2*C/m ; C=M/z
Aluminum hydroxide Al(OH)3 (g/L):

Remarks
Rinsing and conditioning of the pH sensor is crucial to achieve accurate and precise results. In fact, the pH sensor is titrating in a strong alkaline solution (pH > 12). The parameters have been optimized for this specific sample solution. It may be necessary to adapt the method to your sample. The %-content Al2O3 is calculated from the mg/g-content Al(OH)3 (see R4) by multiplying it with a conversion factor from the ratio between M(Al2O3) and M(Al(OH3)) (see R5).
Titration Application M466A-2010

R3 = (Q[2]+QEX)*C/m ; C = M/z, M = 78.00 , z = 3 (see “Comments”)

-

Waste disposal Author, Version
METTLER TOLEDO

After neutralization dispose the sample solution as heavy metals. Cosimo De Caro MSG Anachem, July 2010

-

Page 1 of 7

Instruments

-

T70 / T90 Titration Excellence Analytical Balance, e.g. XP205 Precision Balance, e.g. MS6002S Rondo 20 sample changer 3 additional dosing units 2 x 10 mL DV1010 burette, 2 x 20 ml DV1020 burette PP Titration beakers ME-101974 LabX pro titration software

Accessories

Results
No. 1/6 Comment / ID -Start time 22.07.2010 08:30:39 Sample size and results R1 = R2 = R3 = R4 = R5 = 2/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3 -22.07.2010 08:47:48 R1 = R2 = R3 = R4 = R5 = 3/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3 -22.07.2010 09:04:36 R1 = R2 = R3 = R4 = R5 = 4/6 +25 mKL HO / 30.23g/500mL + 10 mL 3g/60mLNa2CO3 -22.07.2010 09:21:20 R1 = R2 = R3 = R4 = R5 = 5/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3 -22.07.2010 09:38:06 R1 = R2 = R3 = R4 = R5 = 6/6 +25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3 -22.07.2010 09:54:50 R1 = R2 = R3 = R4 = R5 = Statistics Rx R1 R2 R3 R4 R5 Name Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%) n 6 6 6 6 6 Mean value 276.61 84.49 18.25 301.82 39.45 Unit g/L g/L g/L mg/g % s 1.729829 1.292786 0.125167 2.048743 0.267806 srel [%] 0.625 1.530 0.686 0.679 0.679 276.91 85.52 18.38 303.94 39.73 g/L g/L g/L mg/g % Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%) 274.60 84.16 18.21 301.19 39.37 g/L g/L g/L mg/g % Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%) 275.76 85.72 18.18 300.74 39.31 g/L g/L g/L mg/g % Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%) 275.96 82.50 18.10 299.43 39.14 g/L g/L g/L mg/g % Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%) 276.73 85.45 18.19 300.89 39.33 g/L g/L g/L mg/g % Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%) 279.72 83.60 18.42 304.71 39.83 g/L g/L g/L mg/g % Free Caustic NaOH Free Carbonate CaCO3 Content Al(OH)3 (g/L) Content Al(OH)3 (mg/g) Content Al2O3 (%)

+25 mL H2O / 30.23g/500mL + 10 mL 3g/60mLNa2CO3

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Titration Application M466A-2010

Titration curve (1st Titration: NaOH and carbonate)

Sample 1/6 22.07.2010 08:30

Table of measured values (1st Titration: NaOH and carbonate)
Volume mL
0.000 17.143 25.714 30.000 30.200 30.400

Increment mL
NaN 17.143 8.571 4.286 0.200 0.200

Signal pH
13.542 13.295 13.024 12.842 12.794 12.781

Change pH
NaN -0.247 -0.271 -0.182 -0.048 -0.013

1st derive. pH/mL
NaN NaN NaN NaN NaN -0.06

Time s
0 20 57 63 82 85

Temperature °C
25.0 25.0 25.0 25.0 25.0 25.0

------------------------------------------------------------------------------------------------------------------------------------------------------------------------

...
EQP1 39.011 39.151 39.219895 39.248 39.354 39.460 39.579 39.736 39.876 40.056 40.202 40.402 40.602 41.002 41.202 41.402 41.602 41.802 42.002 42.202 42.402 42.595 42.758 42.868 42.971 43.069 43.150 43.211 43.261 43.298 43.334 43.368 43.394 43.404282 43.429 43.450 43.477 43.520 43.559 43.620 43.676 43.756 43.842 43.952

...
0.088 0.140 0.097 0.106 0.106 0.119 0.157 0.140 0.180 0.146 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.200 0.193 0.163 0.110 0.103 0.098 0.081 0.061 0.050 0.037 0.036 0.034 0.026 NaN 0.035 0.021 0.027 0.043 0.039 0.061 0.056 0.080 0.086 0.110

...
11.242 11.114 11.049 11.023 10.922 10.826 10.735 10.618 10.526 10.404 10.321 10.219 10.044 9.968 9.879 9.797 9.712 9.627 9.542 9.442 9.338 9.228 9.109 9.015 8.918 8.811 8.701 8.600 8.493 8.401 8.302 8.191 8.111 8.071 7.975 7.895 7.813 7.691 7.606 7.484 7.395 7.284 7.187 7.085

...
-0.070 -0.128 NaN -0.091 -0.101 -0.096 -0.091 -0.117 -0.092 -0.122 -0.083 -0.102 -0.081 -0.076 -0.089 -0.082 -0.085 -0.085 -0.085 -0.100 -0.104 -0.110 -0.119 -0.094 -0.097 -0.107 -0.110 -0.101 -0.107 -0.092 -0.099 -0.111 -0.080 NaN -0.136 -0.080 -0.082 -0.122 -0.085 -0.122 -0.089 -0.111 -0.097 -0.102

...
-0.86 -0.92 -0.93 -0.93 -0.88 -0.84 -0.79 -0.72 -0.66 -0.60 -0.54 -0.48 -0.41 -0.41 -0.41 -0.41 -0.42 -0.43 -0.45 -0.50 -0.57 -0.67 -0.81 -0.93 -1.11 -1.35 -1.64 -1.94 -2.29 -2.60 -2.93 -3.27 -3.47 -3.47 -3.43 -3.22 -2.91 -2.54 -2.25 NaN NaN NaN NaN NaN

...
220 224 NaN 227 230 234 236 240 243 272 275 278 284 287 290 293 296 299 302 305 309 312 315 318 321 324 327 330 333 336 339 342 345 NaN 348 352 356 360 365 371 376 381 387 393

...
25.0 25.0 NaN 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 NaN 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0 25.0

EQP2

METTLER TOLEDO

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Titration Application M466A-2010

Titration curve (2nd Titration: Aluminum)

Sample 1/6 22.07.2010 08:30

Table of measured values (2nd Titration: Aluminum)
Volume mL Increment mL Signal mV Change mV 1st deriv. mV/mL Time s Temperature oC

--------------------------------------------------------------------------------------------------------------------------------------------------------------------0.000 NaN -191.9 NaN NaN 0 25.0 0.005 0.005 -191.7 0.2 NaN 3 25.0 0.010 0.005 -191.6 0.1 NaN 6 25.0 0.022 0.012 -191.3 0.3 NaN 9 25.0 0.052 0.030 -190.4 0.9 NaN 12 25.0 0.127 0.075 -188.4 2.0 26.57 15 25.0 0.315 0.188 -183.7 4.7 24.46 19 25.0 0.515 0.200 -178.8 4.9 23.88 23 25.0 0.715 0.200 -174.2 4.6 23.24 26 25.0 0.915 0.200 -169.8 4.4 23.22 31 25.0 1.115 0.200 -164.8 5.0 23.99 35 25.0 1.315 0.200 -159.6 5.2 24.70 38 25.0 1.515 0.200 -155.2 4.4 26.05 42 25.0 1.715 0.200 -149.3 5.9 27.88 46 25.0 1.915 0.200 -143.2 6.1 30.89 50 25.0 2.115 0.200 -137.1 6.1 36.57 54 25.0 2.315 0.200 -128.8 8.3 45.60 58 25.0 2.503 0.188 -119.9 8.9 59.88 61 25.0 2.650 0.147 -110.6 9.3 78.62 65 25.0 2.746 0.096 -102.7 7.9 96.22 68 25.0 2.819 0.073 -96.1 6.6 111.74 72 25.0 2.900 0.081 -85.7 10.4 130.48 76 25.0 2.944 0.044 -80.1 5.6 144.01 79 25.0 EQP1 3.002191 NaN -70.0 NaN 158.53 NaN NaN 3.006 0.062 -69.3 10.8 158.46 83 25.0 3.040 0.034 -62.2 7.1 154.14 86 25.0 3.072 0.032 -57.5 4.7 139.57 90 25.0 3.150 0.078 -46.9 10.6 121.06 95 25.0 3.213 0.063 -40.0 6.9 107.18 100 25.0 3.305 0.092 -31.7 8.3 NaN 106 25.0 3.413 0.108 -23.8 7.9 NaN 111 25.0 3.546 0.133 -14.9 8.9 NaN 116 25.0 3.679 0.133 -7.8 7.1 NaN 121 25.0 3.862 0.183 0.7 8.5 NaN 126 25.0

METTLER TOLEDO

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Titration Application M466A-2010

Comments
Principle:

Bauxite contains approximately 30 – 54% alumina (Al2O3). The rest mainly consists of silica, iron oxides, and titanium dioxide. During the Bayer process bauxite is digested by washing with a hot solution of sodium hydroxide, NaOH, at 175°C. The alumina is first converted into aluminum hydroxide, Al(OH)3, which subsequently dissolves in the hydroxide solution according to the chemical equation: Al2O3 + 2 OH- + 3 H2O → 2 [Al(OH)4]-

The resulting, strong alkaline solution is called “Bayer liquor”.

Left: Bauxite powder Middle and right: Digested bauxite solution (Bayer liquor). Note that the digested solution is turbid due to the presence of precipitated iron componds (iron hydroxide).

Titration of Bayer liquor with hydrochloric acid: • Addition of excess sodium gluconate (NaGluc): Al(OH)4- + NaGluc • → Al(OH)3Gluc- + NaOH

Titration with 1 mol/L hydrochloric acid, HCl: 1st Equivalence point: OHCO3
2-

+ +

H3O+ H
+

→ →

2 H2O HCO3-

2nd Equivalence point: HCO3- + • Al(OH)3Gluc• OH- + H3O+ → CO2 + 2 H2O

Addition of excess potassium fluoride: + 6KF → K3AlF6 + 3KOH + Gluc-

The released KOH is titrated with 1 mol/L HCl: H3O+ → 2 H2O

Digestion of bauxite: Generally, a freshly prepared NaOH solution does not contain carbonate. Thus, only one equivalence point can be detected in the first titration with HCl. Carbonate is formed in alkaline solution due to intake of CO2 during a long exposition time to air. To reproduce two equivalence points, the synthetic Bayer liquor was spiked with 10 mL sodium carbonate solution (approx. 3 g Na2CO3/60 mL).

METTLER TOLEDO

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Titration Application M466A-2010

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume [ml] Density Correction factor Temperature General titration T70 / T90 m466 Aluminum content in bauxite Administrator 23.07.2010 16:23:20 23.07.2010 16:23:20 Administrator No None Concentration [mol/L] Volume [mL] Dosing rate [ml/min] Condition 008 Stir Speed [%] Duration [s] Condition 009 Titration (EQP) [2] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed[&] Predispense Mode Waiting time [s] Control Control Titrant addition dE (set value)[mV] dV (min)[ml] dV (max)[ml] Mode dE[mV] dt[s] t (min)[s] t (max)[s] Evaluation and recognition Procedure Threshold[mV/ml] Tendency Ranges Add. EQP criteria Steepest jumps Termination At Vmax[ml] At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Condition 010 Rinse Auxiliary reagent Rinse cycles Vol. per cycle[mL] Position Drain Condition 011 Conditioning Type Interval Position Time [s] Speed [%] Condition 012 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 013 Calculation R2 Result Result unit 30 180 No 30 10 60 No

HCl 1 pH DG115-SC mV No 30 None 0 User Dynamic 8.0 0.005 0.2 Equilibrium controlled 0.5 1 3.0 30.0 Standard 5 Positive 0 Steepest jump 1 5 No No Yes 1 No No No

1 -Fixed volume 5.0 1.0 g/mL 1.0 25.0°C

003 Titration stand (Rondo/Tower A) Type Rondo/Tower A Titration stand Rondo60/1A Lid handling No 004 Dispense (normal) [1] Titrant Concentraition [mol/L] Volume [mL] Dosing rate [ml/min] Condition 005 Stir Speed [%] Duration [s] Condition 006 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Volume [ml] Waiting time [s] Control Control Titrant addition dE (set value)[mV] dV (min)[ml] dV (max)[ml] Mode dE[mV] dt[s] t (min)[s] t (max)[s] Evaluation and recognition Procedure Threshold[pH/ml] Tendency Ranges Add. EQP criteria Termination At Vmax [ml] At potential Potential [pH] Termination tendency At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Condition 007 Dispense (normal) [2] Titrant 30 120 No

Na-gluconate 25 10 60 No

HCl 1 pH DG115-SC pH No 30 Volume 30 15 User Dynamic 6 0.002 0.2 Equilibrium controlled 0.5 1 3.0 30.0 Standard 0.5 Negative 0 No 60 Yes 6 Negative No Yes 2 No No No

Water 1 10 Current position No No

Fix 1 Conditioning beaker 60 30 No

Free Caustic NaOH g/L R1=(Q-Q2)*C/m M/z M[Sodium hydroxide] z[Sodium hydroxide] 2 No Yes No No No

KF

Free Carbonate CaCO3 g/L

METTLER TOLEDO

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Titration Application M466A-2010

Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 014 Calculation R3 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 015 Calculation R4 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 016 Calculation R5 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 017 End of sample 018 Park Titration stand Position Condition

R2=Q2*C/m M/z M[Calcium carbonate] z[Calcium carbonate] 2 No Yes No No No

Content Al(OH)3 (g/L) g/L R3=(Q[2]+QEX)*C/m M/z M[Aluminum trihydroxide] z[Aluminum trihydroxide] 2 No Yes No No No

Content Al(OH)3 (mg/g) mg/g R4=((Q[2]+QEX)*C/30.23)*100 M/z M[Aluminum trihydroxide] z[Aluminum trihydroxide] 2 No Yes No No No

Content AL2O3 (%) % R5=(R4/10)*C 1.30717 M[None] z[None] 2 No Yes No No No

Rondo60/1A Conditioning beaker No

Calculation R4: 30.23 = sample size of bauxite powder 100 = dilution factor (5 mL -> 500 mL)

Calculation R5: 1.30717 = M(Al2O3)/M(Al(OH)3) = 101.96/78.00

METTLER TOLEDO

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Titration Application M466A-2010

METTLER TOLEDO

Application M222-2010

Determination of Boric Acid in Acidic HCl/HF Solutions
Boric acid is determined by titration with sodium hydroxide after addition of mannitol. The titration is monitored by a combined pH glass electrode. Acidic bath, 5 mL

Sample

Preparation and Procedures
- 5 mL acidic bath is diluted with 50 mL deionized water.

Compound

-

Boric acid, B(OH)3 M = 61.83, z = 1 Hydrochloric acid, HCl Hydrofluoric acid, HF

- The sample is titrated with sodium hydroxide to pH 7 (= 0 mV). - This gives the total acid content (HCl, HF) present in the sample. - 20 mL mannitol solution is automatically added to the sample beaker by means of an additional burette. - The sample solution is stirred for 20 s or during a longer time to allow for a complexation reaction between mannitol and boric acid. - The complexation reaction leads to a release of hydrogen ions. - These ions can be titrated with 0.1 mol/L NaOH.

Chemicals

- 50 mL deionized water, - 20 mL mannitol solution, C6H8(OH)6 , c(C6H8(OH)6) = 200 g/L Sodium hydroxide, NaOH, c(NaOH) = 0.1 mol/L

Titrant

Standard

Potassium hydrogen phthalate, KHP,

see e.g. M002

Remarks
- The method was developed on a DL70 titrator and has been adapted for T50/T70/T90 Titration Excellence. - Boric acid is a weak monobasic acid in aqueous solutions. Thus, it cannot be directly titrated using a strong base. - Mannitol, C6H8(OH)6 , forms a stable 1:1 complex with boric acid: B(OH)3 + M → B(OH)2O-M- + H+ - The released hydrogen ions can be titrated with sodium hydroxide solution.

Indication

DGi112-SC or DGi114-SC combined pH glass electrode with movable sleeve Simplified reaction scheme: B(OH)3 + M → B(OH)2O-M- + H+ H3O+ + NaOH → 2 H2O + Na+ where M = C6H8(OH)6

Chemistry

Calculation

Content boric acid (g/L): R = Q*C/m C = M/z

In general: - The addition of mannitol solution allows to avoid volatilization of boron in sample solutions, and to increase the dissociation strength to achieve optimum titration conditions (For more detailed information, see Literature under “Comments”).

Waste disposal

Neutralization with hydrochloric acid before final disposal

Author, Version
METTLER TOLEDO

Dieter Rehwald, MT-Germany,1989 Rev. February 2010 / C. De Caro
Page 1 of 5 Titration Application M222-2010

Instruments

- DL70 Titrator - Balance, e.g. XS205
Other titrators: This method can also be run with the T50/T70/T90 Titration Excellence, and with the DL55, DL58, DL70ES, and DL77 instruments. Minor changes in the methods are required.

Accessories

-

2 x 10 mL DV1010 burettes Additional dosing unit (Tx) ME-51109030, or burette drive (DL5x, DL7x) PP titration beaker ME-101974 Printer

Results
METTLER DL70 Titrator Measured Titrator User 14-Nov-1989 **** 12:44

A001 Borsäure 14-Nov-1989 12:28 SW Version 1.2 RESULTS No 1/1 ID1 4711 Volume 5.0

Results mL 5.179 9.245 11.43 mL mL g/L ml HCl/HF ml Brsaeure Content

Titration curve

METTLER TOLEDO

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Titration Application M222-2010

Table of measured values
Not available

Comments
• Boric acid is used in various market segments and for the most different applications such as e.g. antiseptic, flame retardant, and in nuclear power plants to control the rate of fission. In electroplating and semiconductor industry it is used among other purposes for e.g. surface treatment and metal processing (e.g. nickel baths, boron metal alloys). The acid dissociation constant pKa of boric acid B(OH)3 is 9.14 at 25°C, thus it is a rather weak acid. Boric acid does not dissociate in aqueous solution, but is acidic due to its interaction with water molecules, forming tetrahydroxyborate ions: B(OH)3 + H2O → B(OH)4- + H+ Ka = 5.8x10−10 mol/l; pKa = 9.24

• •

However, the dissociation is not so strong, and therefore the released hydrogen ions can not be directly titrated with a strong base.

Literature: METTLER TOLEDO Application Brochure No. 1, “18 Customer Methods””, ME-724492, 1992. T. Ishikawa, E. Nakamura, “Formation of Boron-mannitol Complex in the Hydrofluoric Acid Solution and a Possibility of the Use of Acids in the Separation of Boron from the Natural rock Samples”, Proc. Japan Acad. 66 No.5 (Ser. B), p. 91, 1990. P. M. Williams and P. M. Strack, “Complexes of Boric Acid with Organic Cis-Diols in Seawater”, Limnology and Oceanography, Vol. 11, No. 3, pp. 401-404, 1966. P. A. Webster, “Determination of Boric Oxide in Glass by Direct Titration”, Journal of the American Ceramic Society, Volume 34 Issue 10, pp 305-309, 1951. Max Hollander, William Rieman, “Titration of Boric Acid in Presence of Mannitol”, Ind. Eng. Chem. Anal. Ed. 17 (9), pp 602–603, 1945.

-

-

-

METTLER TOLEDO

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Titration Application M222-2010

Method
DL70 Titrators: Title Method ID ........................... A001 Title ............................... Borsäure Date/time ........................... 14-Nov-1989 12:28 Sample Number samples ...................... Titration stand ..................... Entry type .......................... Lower limit [mL] .................. Upper limit [mL] .................. ID1 ................................. Molar mass M ........................ Equivalent number z ................ Stir Speed [%] ........................... Time [s] ............................ Titration Titrant ............................. Concentration [mol/L] ............... Sensor .............................. Unit of meas. ...................... Titration mode ...................... Predispensing 1 ................... Volume [mL] .................... Titrant addition .................... dE(set) [mV] ................... dV(min) [mL] ................... dV(max) [mL] ................... dE [mV] ........................ dt [s] ......................... t(min) [s] ..................... t(max) [s] ..................... Endpunktart ......................... Potential [mV,pH,…] ............ Tendency ............................ Maximum volume [mL] ................. Calculation Result name ......................... Formula ............................ Constant ............................ Result unit ......................... Decimal places ...................... Record All results ......................... Table of measured values ............ E – V curve ......................... Dispense Titrant ............................. Concentration [mol/L] ............... Volume [mL] ......................... Stir Speed [%] ........................... Time [s] ............................ Titration Titrant ............................. Concentration [mol/L] ............... Sensor .............................. Unit of meas. ...................... Titration mode ...................... Predispensing 1 ................... Volume [mL] .................... Titrant addition .................... dE(set) [mV] ................... Limits dV ...................... dV(min) [mL] ................. dV(max) [mL] ................. Measure mode ....................... dE [mV] ........................ dt [s] ......................... t(min) [s] ..................... t(max) [s] ..................... Threshold ........................... Maximum volume [mL] ................. Evaluation procedure ................ Calculation Result name ......................... Formula ............................ Constant ............................ Result unit ......................... Decimal places ...................... Calculation Result name ......................... Formula ............................ Constant ............................ Result unit ......................... Decimal places ...................... 50 10 NaOH 0.1 DG112-SC mV EP to volume 1.0 Dynamic 8.0 0.02 0.1 0.5 0.5 2.0 20.0 EPA 0.0 Negative 10.0 mL HCl/HF R=VEQ C=1 mL 3 Yes Yes Yes Mannit 0.0 20.0 50 20 NaOH 0.1 DG112-SC mV EQP to volume 1.0 DYN 8.0 Absolute 0.02 0.2 EQU 1.0 1.0 3.0 30.0 20.0 10.0 Standard mL Brsaeure R2=VEQ[2]+VEX[1] C2=1 mL 3 Content
R3=(Q[2]+QEX[1])*C3/U

Record All results ..........................Yes Table of measured values .............Yes E – V curve ..........................Yes

1 Stand 1 Volume U 1.0 10.0 4711 61.83 1

-------------------------------------------------------------Titration Excellence: 001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Lower limit Upper limit Density Correction factor Temperature Entry

General titration T50/T70/T90 m222 Boric acid Mettler Toledo 01.02.2010 08:00:00 01.02.2010 08:00:10 Administrator No None

1 Acidic solution Volume 1.0 mL 10.0 1.0 g/mL 1.0 25.0°C Before

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Stir Speed Duration Condition 005 Titration (EP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Waiting time Control End point type Tendency End point value Control band Dosing rate(max) Dosing rate(max) Termination At EP Termination delay At Vmax Max. time 006 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics 007 Record Summary Results Raw results Table of meas. values 50% 10 s No

NaOH 0.1 mol/L pH DG115-SC mV No 35% Volume 1.0 10 s Absolute Negative 0.0 mV 100.0 mV 10 mL/min 10 µL/min Yes 10 s 10.0 mL infinity

Consumption HCl/HF mL R1 = VEQ[1] 1 M[None] z[None] 3 No No

C3=M/z g/L 2

No Per sample No Yes

METTLER TOLEDO

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Titration Application M222-2010

Sample data Resource data E - V dE/dV - V log dE/dV - V d2E/dV2 - V BETA – V E - t V - t dV/dt - t T – t E – V & dE/dV – V V – t & dV/dt – t Method Series data Condition 008 Dispense (normal) [1] Titrant Concentration Volume Dosing rate Condition 009 Stir Speed Duration Condition 010 Titration (EQP) [2] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed Predispense Mode Volume Waiting time Control Control Titrant addition dE(set value) dV(min) dV(max) Mode dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs 011 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics 012 Calculation R3 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics

No No Yes No No No No No No No No No No No No No

Mannitol 1 20.0 mL 60.0 mL/min No

013 Record Summary Results Raw results Table of meas. values Sample data Resource data E - V dE/dV - V log dE/dV - V d2E/dV2 - V BETA – V E - t V - t dV/dt - t T – t E – V & dE/dV – V V – t & dV/dt – t Method Series data Condition 014 End of sample

No Per sample No Yes No No Yes No No No No No No No No No No No No No

50% 20 s No

NaOH 0.1 mol/L pH DG115-SC mV No 35% Volume 1.0 10 s User Dynamic 8.0 mV 0.02 mL 0.2 mL Equilibrium controlled 1.0 mV 1 s 3 s 30 s Standard 20 Negative 0 No 20.0 mL No No Yes 1

Consumption boric acid mL R2 = VEQ[2]+VEX[1] 1 M[None] z[None] 3 No No

Boric acid content g/L R3 = (Q[2]+QEX[1])*C/m M/z M[B(OH)3] z[B(OH)3] 2 No Yes

METTLER TOLEDO

Page 5 of 5

Titration Application M222-2010

METTLER TOLEDO Titanium Content in Mining Solutions

Application M467-2010

Determination of titanium content in titanium ore digestion and purification solution.

Sample

Digestion solution from titanium ore (e.g. TiO2) ~ 5 mL Titanium, Ti3+, M = 47.867 g/mol, z = 1

Preparation and Procedures
CAUTION: Work with a lab coat, and wear gloves and safety goggles.

Compound

-

Chemicals

40 mL deionized water 10 mL concentrated H2SO4

Depending on the expected concentration of Ti3+ in the sample solution, the amount of sample is chosen in such a way that the final amount of Ti3+ in the titration vessel is ~ 0.5 mmol. This leads to a titrant consumption of ~ 5 mL, which is approximately half the burette volume. To the sample solution 40 mL deionised water and ~ 10 mL concentrated sulfuric acid are added to make the sample solution acidic enough for the redox reaction between iron and titanium to take place.

Titrant

Ferric ammonium sulfate, NH4Fe(SO4)2 (Fe(III)AS) c(NH4Fe(SO4)2) = 0.1 M

-

Standard

Ascorbic acid, C6H8O6

Indication

DMi140-SC

Remarks Chemistry
Fe3+ + Ti3+ → Fe2+ + Ti4+ The parameters have been optimized for this specific sample. It may be necessary to adapt the method to your sample. Since Ti3+ is a very unstable species, the sample solution should always be prepared freshly. Also make sure to add the titanium solution to the titration beaker only directly before the titration itself. Otherwise loss of titanium can be observed within one sample series because of oxidation by air. The use of an inert gas such as nitrogen could be recommended. Please take care when handling the concentrated sulfuric acid as this will cause severe burns when in contact with skin.

-

Calculation

Ti-Content (g/L): R1 = Q*C/m C = M/z Content (mol/L): R2 = Q*C/m C = 1/z

-

-

Waste disposal

After neutralization of the acid dispose the sample solution as heavy metals. Melanie Nijman, MSG Anachem, June 2010
Page 1 of 4

Author, Version
METTLER TOLEDO

Titration Application M467-2010

Instruments

- T50/T70/T90 Titration Excellence - Balance, e.g. XS205 - Rondo 20 sample changer - 1 x 10 mL DV1010 burette - PP Titration beakers ME-101974 - LabX pro titration software

Accessories

Results
Samples 1/6 2/6 3/6 4/6 5/6 6/6 Results 1/6 2/6 3/6 4/6 5/6 6/6 Titanium solution Titanium solution Titanium solution Titanium solution Titanium solution Titanium solution Comment / ID Titanium solution Titanium solution Titanium solution Titanium solution Titanium solution Titanium solution 5.0 mL 5.0 mL 5.0 mL 5.0 mL 5.0 mL 5.0 mL Rx R1 = R2 = R1 = R2 = R1 = R2 = R1 = R2 = R1 = R2 = R1 = R2 = Statistics Rx R1 R2 Name Content Content n 6 6 Mean value 4.1522 0.08675 Unit g/L mol/L s 0.0210 0.00044 srel [%] 0.505 0.505 Result 4.1367 0.08642 4.1726 0.08717 4.1402 0.08649 4.1297 0.08628 4.1821 0.08737 4.1518 0.08674 g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L g/L mol/L Unit Name Content Content Content Content Content Content Content Content Content Content Content Content

Titration curve

METTLER TOLEDO

Page 2 of 4

Titration Application M467-2010

Table of measured values
Volume mL 0.0000 0.0200 0.0400 0.0600 0.1100 0.2350 0.5475 1.0475 1.5475 2.0475 2.5475 3.0300 3.1870 3.2480 3.4005 3.4695 3.6420 3.6620 3.7120 3.7440 3.7900 3.8415 3.8695 3.8960 3.9205 3.9475 3.9675 3.9875 4.0075 4.0275 4.0475 4.0675 4.1175 4.1375 4.1388 4.1575 4.1775 4.1975 4.2175 4.2430 4.2695 4.3085 4.3685 4.4470 4.5365 Increment mL NaN 0.0200 0.0200 0.0200 0.0500 0.1250 0.3125 0.5000 0.5000 0.5000 0.5000 0.4825 0.1570 0.0610 0.1525 0.0690 0.1725 0.0200 0.0500 0.0320 0.0460 0.0515 0.0280 0.0265 0.0245 0.0270 0.0200 0.0200 0.0200 0.0200 0.0200 0.0200 0.0500 0.0200 NaN 0.0200 0.0200 0.0200 0.0200 0.0255 0.0265 0.0390 0.0600 0.0785 0.0895 Signal mV 127.3 15.0 -55.7 -67.9 -68.1 -67.0 -62.5 -55.6 -49.7 -43.9 -35.7 -21.8 -31.5 -29.6 -20.5 -18.9 -2.0 -2.0 1.2 4.5 10.4 20.3 27.0 34.4 41.4 51.6 61.2 70.0 91.5 111.4 133.1 140.1 206.2 254.7 257.2 292.5 344.2 365.0 376.4 387.0 394.7 402.4 410.9 419.7 426.5 Change mV NaN -112.3 -70.7 -12.2 -0.2 1.1 4.5 6.9 5.9 5.8 8.2 13.9 -9.7 1.9 9.1 1.6 16.9 0.0 3.2 3.3 5.9 9.9 6.7 7.4 7.0 10.2 9.6 8.8 21.5 19.9 21.7 7.0 66.1 48.5 NaN 37.8 51.7 20.8 11.4 10.6 7.7 7.7 8.5 8.8 6.8 1st deriv. mV/mL NaN NaN NaN NaN NaN -164.84 -17.93 13.16 15.36 13.92 14.57 24.96 32.84 35.89 47.54 53.25 99.88 98.15 116.80 122.92 148.23 220.52 259.63 296.47 355.89 457.57 597.72 705.32 765.55 849.06 932.52 1200.09 1654.10 1851.92 1915.87 1856.88 1544.28 1098.89 797.07 593.63 NaN NaN NaN NaN NaN Time s 0 36 66 86 89 92 96 100 104 108 113 117 136 138 142 157 162 168 180 188 196 210 221 232 244 257 260 269 272 275 278 291 304 308 NaN 313 343 351 354 357 360 363 366 370 373

EQP1

Comments
--

METTLER TOLEDO

Page 3 of 4

Titration Application M467-2010

Method
001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Volume [mL] Density [g/mL] Correction factor Temperature [°C] Condition General titration T50 / T70 / T90 MNxxxE Titanium content Administrator 01/06/2010 18:11:34 02/06/2010 08:45:39 Administrator No None 008 Calculation R2 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer Condition 009 Rinse Auxiliary reagent Rinse cycles Vol. per cycle[mL] Position Drain Condition 010 Conditioning Type Interval Position Time [s] Speed [%] Condition 011 End of sample F(III)AS 0.1 mV DM140-SC mV No 30 None 5 User Dynamic 8.0 0.02 0.2 Equilibrium controlled 0.5 2 3 10 Standard 1500 None 0 No No

1 Titanium Solution Fixed volume 5.0 1.0 1.0 25.0°C

Content mol/L R2=Q*C/m 1/z M[Titanium] z[Titanium] 5 No Yes No No No

003 Titration stand (Rondo/TowerA) Type Rondo/Tower A Titration stand Rondo60/1A Lid handling No 004 Stir Speed [%] Duration [s] Condition 005 Titration (EQP) [1] Titrant Titrant Concentration [mol/L] Sensor Type Sensor Unit Temperature acquisition Temperature acquisition Stir Speed [%] Predispense Mode Wait time [s] Control Control Titrant addition dE (set value) [mV] dV (min) [mL] dV (max) [mL] Mode dE [mV] dt [s] t (min) [s] t (max) [s] Evaluation and recognition Procedure Threshold [mV/mL] Tendency Ranges Add. EQP criteria Termination At Vmax [mL] At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Condition 007 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical func. Send to buffer 30 10 No

Water 1 15 Current position No No

Fix 1 Conditioning beaker 10 30 No

10.0 No No Yes 1 No No No

Content g/L R1=Q*C/m M/z M[Titanium] z[Titanium] 4 No Yes No No

METTLER TOLEDO

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Titration Application M467-2010

METTLER TOLEDO
Determination of Cobalt Content in Alloys

Application M458-2010

The cobalt content in alloys is determined by redox titration in strong acid solution with potassium hexacyanoferrate K3Fe(CN)6 as a titrant. The potential change is monitored by a combined platinum ring electrode.

Sample

Metal alloy, 0.15 g 6-13% Co content Cobalt, Co M = 58.933; z = 1

Preparation and Procedures
CAUTION: Cyanide is toxic! A too low pH value leads to the formation of HCN gas which is toxic. Thus, work in a fume hood, use safety goggles and wear gloves. Sample dissolution: - 0.15 g metallic alloy is placed in a suitable container for dissolution e.g. a platin crucible. - 5 mL concentrated nitric acid is added, together with 2-3 mL hydrofluoric acid. - The solution is heated until alloy is dissolved. - After cooling down to room temperature, 10-15 mL deionized water is added. - The sample solution in poured into a polypropylene titration beaker. Cobalt is now present as Co(II) Titration: - 10 mL 50% ammonium citrate is added to the sample - 20 mL ammonium hydroxide solution is added to the sample. - Add 10-20 mL deionized water. - Start titration.

Compound

Chemicals

85% Nitric acid, HNO3 48% Hydrofluoric acid, HF 50% Ammonium citrate, (NH4)3C6H5O7 30% Ammonium hydroxide, NH4OH Deionized water

Titrant

Potassium hexacyanoferrate, K3 Fe(CN)6, c(KFe(CN)6) = 0.017 mol/L Cobalt chloride, CoCl2 DMi140-SC combined redox electrode
Co(NH3)6 + Fe(CN)6 Co(NH3)63+ + Fe(CN)64Simplified: Co2+ + Fe 3+ →
3+ 2+ 3-

Standard Indication

Remarks
- The method parameters have been developed and optimized for this application. It may be necessary to adapt the method to your sample.
2+

Chemistry

Co

+

Fe

- Clean the electrode thoroughly after each sample. If necessary, clean the metal ring of the electrode with a paper tissue.

Calculation

Content (DL5x) • R1 = Q*C/m • C = M/(10*z)

Literature: - ISO 9389:1989 (E), “Nickel alloys- Determination of cobalt content – Potentiometric titration with potassium hexacyanoferrate(III)”, www.iso.org . - H. Poppe, G. Den Boef, “Photometric titration of cobalt with hexacyanoferrate(III)”, Talanta, Vol. 12, Issue 6, 1965, pp 625-637. - E. Norkus, “Potentiometric titration of Co(II) in presence of Co(III)”, Talanta, Vol. 47 (1998), pp 1297-1301.

Waste disposal

Cyanide solutions. CAUTION: Cyanide is toxic!
Lee Hyun Jung, MT-Korea, Dec 2003 Revised January 2010 / C. De Caro

Author, Version
METTLER TOLEDO

Page 1 of 5

Titration Application M458-2010

Instruments

- DL50 Graphix Titrator - AT261 Balance
This method can also be run with the G20 and T50/70/90 Titration Excellence (minor adaptations in their method), and with the DL53/DL55/DL58, and DL67/70ES/77 instruments.

Accessories

- 1 x 10 mL DV1010 burette - Titration beaker ME-101974 - Printer

Results
Alloy Theoretical Co-content % Results % Std. deviation % srel % Comments

G10E

6.0

Average: KPM25P 10.2

5.964 5.952 5.956 5.973 5.961 9.888 10.091 10.018 9.972 10.012 9.996 7.375 7.086 6.869 6.600 6.329 6.852 12.821 12.576 12.541 12.548 12.316 12.560 12.814 12.807 12.844 12.845 12.828

Ammonium citrate: 7.5 mL Ammonium hydroxide: 17.5 mL

0.009287

0.156
Ammonium citrate: 7.5 mL Ammonium hydroxide: 17.5 mL

Average: CN20 7.8

0.07417

0.742
Ammonium citrate: 7.5 mL Ammonium hydroxide: 17.5 mL

Average: FA1 13.0

0.407924

5.954
Ammonium citrate: 7.5 mL Ammonium hydroxide: 17.5 mL

Average:

0.179177

1.426
Ammonium citrate: 10 mL Ammonium hydroxide: 20 mL

Average:

0.019841

0.155

METTLER TOLEDO

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Titration Application M458-2010

Titration curve

KPM25P sample 1/5

Table of measured values

Volume mL ET1 0 0.02 0.04 0.08 … … 13.52 13.72 13.92 14.12 14.276 14.4 14.491 14.568 14.632 14.686 14.731 14.775 EQP1 14.812 14.843 14.88

Increment mL 0.02 0.02 0.04 … … 0.2 0.2 0.2 0.2 0.156 0.124 0.091 0.077 0.064 0.054 0.045 0.044 0.037 0.031 0.037

Signal mV -125.3 -125.1 -125 -125 … … -58.5 -53.1 -47 -38.9 -30.7 -22 -14.2 -6 2.1 10.3 17.8 26.1 34.3 41.1 49.2
KPM25P sample 1/5

Change mV 0.2 0.1 0 … … 4.3 5.4 6.1 8.1 8.2 8.7 7.9 8.1 8.1 8.2 7.5 8.3 8.2 6.8 8.1

1st deriv. mV/mL 9.7 6.5 0 … … 21.6 26.8 30.4 40.7 52.6 69.8 86.6 105.7 126.2 152 166.6 189.5 221.8 218.9 218.3

Time min:s 0:03 0:06 0:09 0:12 … … 5:01 5:06 5:12 5:19 5:26 5:34 5:42 5:51 5:59 6:09 6:18 6:25 6:34 6:43 6:51

METTLER TOLEDO

Page 3 of 5

Titration Application M458-2010

Comments
Redox potential of cobalt (acidic solution) Co2+ + 2 eCo3+ + e= = Co Co2+ E = - 0.277 V E = + 1.808 V

Co2+ ion is stable in acidic solution. Additional titration methods for the determination of cobalt 1. Redox titration of Co(II): Oxidation of Co(II) to Co(III) with a known excess of sodium chromate (Na2CrO4) and back titration with iron(II) ammonium sulfate, (NH4) 2FeSO4. Indication: DMi140-SC (combined platinum ring electrode) Reagents: - Sodium chromate (Na2CrO4), 0.033 mol/L - Iron(II) ammonium sulfate (NH4) 2FeSO4 , 0.1 mol/L - Ethylenediamine C2H4(NH2)2 , 0.1 mol/L - Sulfuric acid 50%, H2SO4 Procedure: Add to sample 10 mL 0.1 mol/L ethylenediamine, 4 mL 0.033 mol/L sodium chromate, and 5 mL 50% sulfuric acid. Titrate with 0.1 mol/L (NH4) 2FeSO4 (Determ. limits: 25 mg Co per sample). 2. Precipitation titration of Co(II) Precipitate Co(II) with an excess of cyanide solution and back titrate the cyanide excess with silver nitrate. Indication: DMi141-SC (combined silver ring electrode) Reaction: - Precipitation of Co(II) with an excess of cyanide: Co2+ + 5 CN- → [Co (CN)5]3- Back titration of cyanide excess (two-step titration): Ag+ + 2 CN→ [Ag (CN)2]+ [Ag (CN)2] + Ag → 2 AgCN The titration curve shows two inflection points corresponding to the two steps of titration 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 solution remains clear. First excess of silver ions causes formation of a white precipitate indicating the equivalence point: Ag+ + [Ag(CN)2]-→ Ag[Ag(CN)2]

1 mole Ag-ions : 2 moles CN-ions. A factor 2 has to be included in the calculation (see M196). Procedure: Dilute the sample in 50 mL water and add 20 mL 0.1 mol/L potassium cyanide KCN. Back titrate with 0.1 mol/L silver nitrate AgNO3 to the second EQP. 3. Complexometric titration of Co(III/II) Direct titration of cobalt Co3+ is performed in ammonia-containing solution with EDTA and murexide as indicator. The endpoint is given by a sharp color change from yellow to red/violet. Indication: Photometric sensor, e.g. DP5 Phototrode™ at 520 nm. Procedure: The pH of the acidic cobalt solution (max. 25 mg/100 mL sample) is adjusted to approximately pH 6. Subsequently, murexide is added to the sample beaker, whereby an orange color is appearing. Ammonia solution is added until the color has changed to yellow. The solution has to be slightly basic (e.g. pH 8). At that point, the sample solution is titrated with EDTA. During titration, the solution becomes acidic due to release of hydrogen ions H+ from EDTA, and the color is vanishing back from yellow to orange. To avoid it, it is necessary to add some drops of ammonia during titration to get back the yellow color. Important: do not add too much ammonia since amine complexes of cobalt are formed.

METTLER TOLEDO

Page 4 of 5

Titration Application M458-2010

Method
DL5x Titrator Method 1 Version Cobalt II 03-Dec-2003 Titration Excellence 001 Title Type General titration Compatible with T50 / T70 / T90 ID 1 Title Cobalt II Author METTLER TOLEDO Date/Time 01.03.2010 15:00:00 Modified -Modified by -Protect No SOP None 002 Sample Number of IDs 1 ID 1 -- 1 Entry type Weight Lower limit 0.0 g Upper limit 2.0 g Density 1.0 g/mL Correction factor 1.0 Temperature 25.0°C 003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Stir Speed 40% Duration 20 s 005 Titration (EQP) [1] Titrant Titrant K3Fe(CN)6 Concentration 0.017 mol/L Sensor Type mV Sensor DM140-SC Unit mV Temperature acquisition Temperature acquisition No Stir Speed 40% Predispense Mode None Wait time 0 s Control Control User Titrant addition Dynamic dE(set) 8.0 dV(min) 0.02 mL dV(max) 0.2 mL Meas. val. acquisition Equilibrium controlled dE 0.5 mV dt 1.0 s t(min) 3.0 s t(max) 30.0 s Evaluation and recognition Procedure Standard Threshold 30 mV/mL Tendency Positive Ranges 0 Add. EQP criteria No Termination At Vmax 20.0 mL At potential No At slope No After number of recognized EQPs No Combined termination criteria No 006 Calculation R1 Result Co content Result unit % Formula R=Q*C/m Constant C=M/(10*z) M M[Co] z z[Co] Decimal places 3 ... 007 Calculation R2 Result Consumption Result unit mL Formula R2=VEQ Constant C=1 M M[None] z z[None] Decimal places 3 ... 008 Record . . . . 009 End of sample

8:35

Title Method ID .......................... Title .............................. Date/time .......................... Sample Sample ID .......................... Entry type ......................... Lower limit [g] ................ Upper limit [g] ................ Molar mass M ....................... Equivalent number z ................ Titration stand .................... Temperature sensor ................. Stir Speed [%] .......................... Time [s] ........................... EQP titration Titrant/Sensor Titrant ........................ Concentration [mol/L] .......... Sensor ......................... Unit of meas. .................. Predispensing ...................... Titrant addition ................... dE(set) ........................ dV(min) [mL] ................... dV(max) [mL] ................... Measure mode ....................... dE [mV] ........................ dt [s] ......................... t(min) [s] ..................... t(max) [s] ..................... Recognition Threshold ...................... Steepest jump only ............. Range .......................... Tendency ....................... Termination at maximum volume [mL] ......... at potential ................... at slope ....................... after number EQPs .............. n = ...................... comb. termination criteria ..... Evaluation Procedure ...................... Potential 1 ................... Potential 2 ................... Stop for reevaluation ......... Calculation Formula ........................... Constant ........................... Decimal places ..................... Result unit ........................ Result name ........................ Statistics ........................ Calculation Formula ........................... Constant ........................... Decimal places ..................... Result unit ........................ Result name ........................ Statistics ........................ Report Output unit ....................... Results ............................ All results ........................ Raw results ........................ Table of measured values ........... Sample data ........................ E - V curve ........................ dE/dV – V curve .................... d2E/dV2 – V curve ................... log dE/dV – V curve... ............. E – t curve ........................ V – t curve ........................ dV/dt - t curve ...................

1 Cobalt II 03-Dec-2003

8:35

Weight 0.0 2.0 58.933 1 Stand 1 Manual 40 20

K3Fe(CN)6 0.017 DM140-SC mV No Dynamic 8.0 0.02 0.2 Equilibrium controlled 0.5 1.0 3.0 30.0 30.0 No No Positive 20.0 No No Yes 1 No Standard No No No R1=Q*C/m C1=M/(10*z) 3 % Co content Yes R2=VEQ 3 mL Consumption No Printer Yes Yes No Yes No Yes Yes No No No No No

METTLER TOLEDO

Page 5 of 5

Titration Application M458-2010

METTLER TOLEDO

Application M292-2010

Determination of Uranium according to Modified Davies-Gray Method
Uranium is determined by indirect titration using potassium dichromate according to the modified method of Davies and Gray. This application has been developed based on standard ASTM C1267-06, but it does not replace the standard used.

Sample

Uranium solution -U(VI), U(IV)- , 2 mL Uranium, U M = 238.03 g/mol , z = 1

Preparation and Procedures
CAUTION: Work under appropriate safety conditions.
See “Comments” for preparation of reagents. The dispensing of reagents is completely automated: - 2 mL acid sample are added into the titration beaker. Uranium is present as UO22+ (VI) or UO2+ (IV) in solution. - 2.5 mL sulphamic acid is added by a burette. Sulphamic acid destroys nitrous acid which can interfere (reducing agents). - A second burette dispenses 15 mL H3PO4/Fe(II) solution. Ferrous ions reduce U6+ to U4+. Concentrated phosphoric acid complexes U6+ to force completion of reaction. - A third burette dispenses 3.4 mL HNO3/Sulphamic acid/Molybdate solution. Excess Fe(II) is destroyed using concentrated nitric acid with ammonium molybdate acting as a catalyst. This leads to NO and NO2 which are neutralized with sulphamic acid. - After 300 s of stir time, 34 mL H2SO4/vanadyl solution is added to the sample by means of a peristaltic pump. - All uranium is now present as U4+. This could be titrated directly with dichromate but the kinetics is very slow. Thus, vanadyl solution is added to the sample solution. U4+ reacts with vanadyl, VO2+ giving V3+.

Compound

Chemicals

- 1 and 1.5 M Sulfamic acid, (NH2)SO3H - 85% Orthophosphoric acid, H3PO4 - 70% Nitric acid (sp. gr. 1.42), HNO3 - Iron(II)sulfate hydrate, FeSO4*7H2O, - 98% Sulfuric acid (sp. gr. 1.84) H2SO4, - Vanadyl sulfate, VOSO4, - Ammonium molybdate, (NH4)6Mo7O24*4H2O

Titrant

Potassium dichromate, K2Cr2O7 c(⅓ K2Cr2O7) = 0.0135 mol/L

Standard Indication

(CH2NH3)2SO4*FeSO4*4H2O
(see M031, Brochure 9)

DMi140-SC (Pt ring) combined redox electrode 1) Reaction of V with U4+: U4+ + 2 VO2+ → UO22+ + 2 V3+ 2) Titration of vanadium: Cr2O72-+ 6 V3++ 2 H+ → 2 Cr3++ 6 VO2+ + H2O

Chemistry

- V3+ can be now titrated with potassium dichromate
according to equation 2 (see “Chemistry”).

Remarks
Literature: 1. ASTM C1267-06, “Standard Test Method for Uranium by Iron (II) Reduction in Phosphoric Acid Followed by Chromium (VI) Titration in the Presence of Vanadium”, 2006. 2. ISO 7097-1:2004, “Nuclear fuel technology -- Determination of uranium in solutions, uranium hexafluoride and solids -- Part 1: Iron(II) reduction/potassium dichromate oxidation titrimetric method”, 2004. 3. Davies, W., Gray, W., Talanta 11 (1964), p. 1203. 4. Eberle, A.R., Lerner, M.W., Goldbeck, C.G., Rodder, C.J., NBL Report 252 (1970). 5. Karekar, C.V., Chander, K., Nair, G.M., Natarajan, P.R., J. Radioanal. Nucl.Chem.Letters 107(5), pp. 297-305, 1986.
Page 1 of 5 Titration Application M292-2010

Calculation

U content (g/L): R1 = Q*C/m C = M/z

Waste disposal

Disposal as radioactive waste (uranium waste)

Author, Version
METTLER TOLEDO

Russel May, MT-AUS, Feb 1994 Revised February 2010

Instruments

- T70/T90 Titration Excellence with LabX titration - XS205 Balance
Other titrators: This method can be also run with the DL70ES and DL77 instruments.

Accessories

-

4 x 10 mL DV1010 burettes + dosing tube adapter 4 to 1 ME-51108356 3 dosing unit ME-51109030 PP titration beaker ME-101974 SP250 Peristaltic pump ME-51108016

Comments
Principle: Uranium samples are generally strong acid solution containing e.g. nitric acid used for dissolution of the sample. Pure uranium, uranium alloys, UO2 powders and pellets, U3O8, U/Zr, U/Al, and so on can be dissolved using strong acid mixtures of HNO3, HF and HCl in various ratio. Dissolved uranium ions are present in the sample solution as U(IV) and U(VI), e.g. U4+ and U6+. Uranium (VI) is reduced to uranium (IV) by excess iron (II) in concentrated phosphoric acid containing sulfamic acid. The excess amount of iron Fe(II) is selectively oxidized by nitric acid (HNO3) in the presence of a molybdenum(VI) catalyst. The nitrogen oxides (NO, NO2) formed during reduction of Fe (II) are neutralized by sulfamic acid. This is necessary since they are reducing agents and thus they interfere with the analysis. After the addition of a vanadium (IV) solution, uranium (IV) reacts with it leading to vanadium (III). Vanadium (III) is titrated with chromium (VI) since the direct titration of U (IV) is very slow.

-

Preparation of reagents: 1. 1 and 1.5 mol/L sulfamic acid solutions, (NH2)SO3H. Sulfamic acid is used to neutralize nitrogen oxides. 2. Orthophosphoric acid solution, H3PO4: Add 2 mL 0.1 mol/L K2Cr2O7 solution and fill up to 500 mL with 85% H3PO4. 3. Ferrous sulfate solution: - Add 50 mL 98% H2SO4 to 350 mL H2O and stir. - Add 140 g FeSO4*7H2O, stir and cool to room temperature. - Dilute to 500 mL with H2O. 4. 0.9 M sulfuric acid, H2SO4 5. H3PO4/Fe2+ solution: - Add 65 mL of ferrous sulfate solution (3) to 500 mL orthophosphoric acid solution (2), and mix well. This solution reduces all the present U6+ to U4+ with excess Fe2+. 6. 8 M HNO3/Sulfamic acid/Ammonium molybdate solution: - Dissolve 2 g ammonium molybdate in 200 mL H20. - Add 250 mL 70% HNO3 and cool down to room T. - Add 50 mL 1.5 M sulfamic acid. - Dilute to 500 mL with H2O. Nitric acid neutralizes excess Fe(II) and ammonium molybdate acts as a catalyst. 7. 0.9 mol/L H2SO4/VOSO4 solution: - Add 0.5 g VOSO4 to 500 mL 0.9 mol/L H2SO4 .This solution has to be prepared weekly. 8. Potassium dichromate titrant, K2Cr2O7: - M(K2Cr2O7) = 294.185 g/mol , c(1/3 K2Cr2O7) = 0.0135 mol/l - Dissolve approx. 1.32 g in 1 L volumetric flask, and dilute with water up to the mark.

METTLER TOLEDO

Page 2 of 5

Titration Application M292-2010

Chemical equations
In concentrated phosphoric acid solution U(VI) is reduced to U(IV): UO22+ • + 2 Fe2+ + 4 H+ → U4+ + 2 Fe3+ + 2 H2O

Excess iron (II) is selectively oxidized by nitric acid (HNO3) in the presence of a molybdenum(VI) catalyst. 3 Fe2+ Fe2+ + + NO3NO3+ + 4 H+ 2 H+ → → 3 Fe3+ + Fe3+ + NO NO2 + + 2 H2O H2O

The nitrogen oxides (NO, NO2) formed during reduction of Fe(II) are neutralized by sulfamic acid. This is necessary since they are reducing agents and thus they interfere with the analysis. After the addition of a vanadium (IV) solution, uranium (IV) reacts with it leading to vanadium (III). U4+ + 2 VO2+ → UO22+ + 2 V3+

Vanadium (III) is titrated with chromium(VI) since the direct titration of U(IV) is very slow. Cr2O72+ 6 V3+ + 2 H+ → 2 Cr3+ + 6 VO2+ + H2O

This reaction is equivalent to: Cr2O72+ 3 U4+ + 2 H+ → 2 Cr3+ + 3 UO22+ + H2O

Therefore: Note:

1 mole Cr2O72- corresponds to 3 mole U4+, and z = 3 for potassium dichromate.

In diluted phosphoric acid solution the following reactions take place: U4+ Fe2+ + + 2 Fe3+ + VO2+ + 2 H2O → 2 H+ → UO22+ + Fe3+ + 2 Fe2+ V3+ + + 4 H+ H2O

Therefore, it is necessary that the phosphoric acid solution is highly concentrated.

Additional remarks
This application allows for the titration of 20 up to 200 mg uranium in a sample. Systematic errors can arise if part of the VO2+ is oxidized by air to V5+. To prevent this, the vanadyl solution should be prepared in acid medium and frequently checked for V5+. To make sure that no errors can occur due to the presence of nitrogen oxides remaining after the Fe2+-NO3- reaction (oxidation of Fe(II) to Fe(III) with nitrate ions), a stream of CO2 gas is passed into the sample solution during analysis. This will remove the oxides. Eberle (see “Remarks”, Literature ref. no. 4) has adapted the titration method of Davies and Gray to achieve a faster method. This method is based on the Modified Davies-Gray titration as given in ASTM Standard C1267-06. This application does not replace the ASTM C1267-06 standard.

-

METTLER TOLEDO

Page 3 of 5

Titration Application M292-2010

Method
Titration Excellence 001 Title Type Compatible with ID Title Author Date/Time Modified at Modified by Protect SOP 002 Sample Number of IDs ID 1 Entry type Lower limit Upper limit Density Correction factor Temperature Entry Stir Speed Predispense Mode Waiting time Control Control Titrant addition dE (set value) dV (min) dV (max) Mode dE dt t (min) t (max) Evaluation and recognition Procedure Threshold Tendency Ranges Add. EQP criteria Termination At Vmax At potential At slope After number of recognized EQPs Number of EQPs Combined termination criteria Accompanying stating Accompanying stating Condition Condition 013 Calculation R1 Result Result unit Formula Constant C= M z Decimal places Result limits Record statistics Extra statistical functions Send to buffer Condition 014 End of sample 35% None 0 s User Dynamic 8 mV 0.02 mL 0.2 mL Equilibrium controlled 0.5 mV 1 s 3 s 30 s Standard 150 Positive 0 No 15 mL No No Yes 1 No No No

General titration T70 / T90 M292 U content Mettler Toledo 01.03.2010 10:00:00 01.03.2010 10:00:10 Administrator No None

1 Uranium Volume 0.0 mL 2.0 mL 1.0 g/mL 1.0 25.0°C Before

003 Titration stand (Manual stand) Type Manual stand Titration stand Manual stand 1 004 Dispense Titrant Concentration Volume Dosing rate Condition 005 Stir Speed Duration Condition 006 Dispense Titrant Concentration Volume Dosing rate Condition 007 Stir Speed Duration Condition 008 Dispense Titrant Concentration Volume Dosing rate Condition 009 Stir Speed Duration Condition 010 Pump Auxiliary reagent Volume [mL] Condition 011 Stir Speed Duration Condition 012 Titration (EQP) [1] Titrant Titrant Concentration Sensor Type Sensor Unit Temperature acquisition Temperature acquisition 70% 60 s No Sulphuric/vanadyl 34.0 No 20% 300 s No 30% 30 s No 15% 30 s No

Sulfamic acid 1.0 mol/L 2.5 mL 60.0 mL/min No

H3PO4/Ferrous 1.0 mol/L 15.0 mL 60.0 mL/min No

U content g/L R1=Q*C/m M/z M[Uranium] z[Uranium] 5 No Yes No No No

HNO3/AmmMolybdate 1.0 mol/L 3.4 mL 60.0 mL/min No

Note: 1. The method can be easily modified to be run on T50 and T70 Titration Excellence instruments. 2. 3. M[Uranium]=238.030 g/mol, z[Uranium]=1 M[K2Cr2O7]=294.185 g/mol, z[K2Cr2O7]=3

1/3 K2Cr2O7 0.0135 mol/L mV DM140-SC mV No

METTLER TOLEDO

Page 4 of 5

Titration Application M292-2010

DL70ES and DL77 Titrators Method T003 Version U by Davies Gray 15-Feb-1994 11:50

Remarks: 1. The original version of this method has the following calculation. Calculation Result name . Formula . . . Constant . . . Result unit . Decimal places With Titration Titrant . . . . . . . . . . . . . . K2Cr2O7 Concentration [mol/L] . . . . . . . 0.0042

Title Method ID . . . . . . . . . Title . . . . . . . . . . . Date/time . . . . . . . . . Sample Number samples . . . . . . . Titration stand . . . . . . Entry type . . . . . . . . . Lower limit [mL] . . . . Upper limit [mL] . . . . ID 1 . . . . . . . . . . . . Molar mass M . . . . . . . . Equivalent number z . . . . Instruction Instruction . . . . . . . . > . . . . . . . . . . . . . > . . . . . . . . . . . . . Dispense Titrant . . . . . . . . . . Concentration [mol/L] . . . Volume [mL] . . . . . . . . Stir Speed [%] . . . . . . . . . Time [s] . . . . . . . . . . Dispense Titrant . . . . . . . . . . Concentration [mol/L] . . . Volume [mL] . . . . . . . . Stir Speed [%] . . . . . . . . . Time [s] . . . . . . . . . . Dispense Titrant . . . . . . . . . . Concentration [mol/L] . . . Volume [mL] . . . . . . . . Stir Speed [%] . . . . . . . . . Time [s] . . . . . . . . . . Pump Auxiliary reagent . . . . . Volume [mL] . . . . . . . . Stir Speed [%] . . . . . . . . . Time [s] . . . . . . . . . . Titration Titrant . . . . . . . . . . Concentration [mol/L] . . . Sensor . . . . . . . . . . Unit of meas. . . . . . . . Titration mode . . . . . . . Titrant addition . . . . dE(set) [mV] . . . . . Limits dV . . . . . . dV(min) [mL] . . . dV(max) [mL] . . . Measure mode . . . . . . dE [mV] . . . . . . . dt [s] . . . . . . . t(min) [s] . . . . . t(max) [s] . . . . . Threshold . . . . . . . . EQP range . . . . . . . . Limit A [mV,pH,...] . Limit B [mV,pH,...] . Maximum volume [mL] . . . Termination after n EQPs n = . . . . . . . . . Evaluation procedure . . Steepest jump only . . . Calculation Result name . . . . . . . . Formula . . . . . . . . . . Constant . . . . . . . . . . Result unit . . . . . . . . Decimal places . . . . . . . Statistics Ri (i=index) . . . . . . . . Standard deviation s . . . . Rel. standard deviation srel Record Output unit . . . . . . . . Results last sample . . . .

. . . . T003 . . . . U by Davies Gray . . . . 15-Feb-1994 11:50 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 1 Stand 1 Volume U 0.0 2.0 Uranium 238.03 1 2.

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

. . . . .

Uranium R=VEQ*C/U C=5 g/L 3

. . . . Aliquot sample . . . . . . . . . . . . Sulphamic acid . . . . 1.0 . . . . 2.5 . . . . 10 . . . . 30 . . . . H3PO4/Ferrous . . . . 1.0 . . . . 15.0 . . . . 30 . . . . 30 . . . . HNO3/Amm molyb . . . . 1.0 . . . . 3.4 . . . . 30 . . . . 300 . . . . Sulphuric /vanad . . . . 34.0 . . . . 70 . . . . 60 . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . K2Cr2O7 0.0042 DM140-SC mV EQP DYN 8.0 Absolute 0.02 0.2 EQU 0.5 1.0 3.0 30.0 150.0 Yes -1000 1000 15.0 Yes 1 Standard Yes Uranium R=(Q*C)/U C=M/z g/L 5

The content is calculated directly form the titrant consumption to the EQP (VEQ). Thus, it seems that a conversion factor in mg U/mL titrant has been used as a titer for the titrant. This conversion factor may be given in the constant C=5.

. . . . R1 . . . . Yes . . . . Yes . . . . Printer . . . . Yes

METTLER TOLEDO

Page 5 of 5

Titration Application M292-2010

This application bulletin represents selected, possible application examples. These have been tested with all possible care in our lab with the analytical instrument mentioned in the bulletin. The experiments were conducted and the resulting data evaluated based on our current state of knowledge. However, the application bulletin does not absolve you from personally testing its suitability for your intended methods, instruments and purposes. As the use and transfer of an application example are beyond our control, we cannot accept responsibility therefore.

When chemicals and solvents are used, the general safety rules and the directions of the producer must be observed.

Selected Applications for Titration in Metals Mining

This brochure contains dedicated applications for the determination of metals in various mining samples. The titration analyses of ferrous and base metals as well as precious metals such as gold and silver are described in a detailed and comprehensive way that allows easy adaptation to the specific sample. In addition, the titration of auxiliary reagents frequently used in mining engineering such as cyanide salts is presented. METTLER TOLEDO offers you various powerful tools for titration in metals mining which are meant to facilitate your content determination analyses and to contribute to reliable results over the whole lifetime of your instrument.

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