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Version: 09

PMP AG

Doc.-No.: 3152

DATA SHEET

SAP-No.: 1679919

Silverlume PLUS

IMDS-No.: 757767

Bright Silver for decorative and technical applications

CONTENTS

1.
2.
3.
4.
5.
6.
7.
8.
11.

12.
13.
14.
15.
16.

Process Information............................................................................................................................... 2
Equipment............................................................................................................................................. 2
Working Parameters.............................................................................................................................. 3
Make-Up................................................................................................................................................ 3
Make-Up Sequence............................................................................................................................... 4
Operating Conditions............................................................................................................................. 5
Maintenance.......................................................................................................................................... 5
Process Control..................................................................................................................................... 6
Pre-treatment Recommendations.......................................................................................................... 8
Equipment........................................................................................................................................ 8
Make-Up........................................................................................................................................... 8
Maintenance..................................................................................................................................... 9
Post-Treatment...................................................................................................................................... 9
SAP No. for Make - Up and Maintenance Products...............................................................................9
General Safety Precautions................................................................................................................... 9
Recommendations for Wastewater Treatment.....................................................................................10
Analytical Instructions.......................................................................................................................... 12
Silverlume B Plus by LC................................................................................................................. 12
Determination of Carbonate by Titration of the Precipitated Barium Carbonate.............................15
Determination of Carbonate by Direct Titration...............................................................................17
Determination of the Content of Free Cyanide by Titration.............................................................19
Silver in cyanidic silver baths by F-AAS.......................................................................................... 21
Determination of Silver with Ammonium Thiocyanate by Titration..................................................24

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Version: 09

Silverlume PLUS

Doc.-No.: 3152

Bright Silver for decorative and technical applications

1. Process Information

Silverlume PLUS is a bright silver plating process, which is extremely versatile and simple to control.

Silverlume PLUS provides brilliant white deposits from both rack and barrel applications and can be
used for all decorative and industrial requirements.

Silverlume PLUS provides uniform bright white deposits with typical hardness value of 80 HV 0.15 +/10 % and electrical resistivity value of approx 1.7/cm.

Silverlume PLUS is based on an organic based brightener system that may also provide some
corrosion protection benefits.

2. Equipment
Tanks

PVC, Polyethylene, Polypropylene as well as PVC /


Polyester composite material

Agitation

Ideally cathode agitation of 2 4 metres/ minute with a


preferred stroke length of 8 10 cm at a rate of 10 to 20
cycles per minute

Exhaust

Essential

Filtration

Continuous filtration, through a 5 m polypropylene filter


cartridge, is required. As a guide, a flow rate of 1 2 times
tank volume per hour is recommended.

Bath temperature

15 - 25 C
Higher temperatures will restrict the effective plating range.

Anodes

Pure silver, 99.9% minimum


The anode area should be as large as possible.
Inert anodes should not be used.

Anode bags

Anode bagging is strongly recommended, using either 'boiled


nettle cloth' or an appropriate synthetic material.

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Silverlume PLUS

Doc.-No.: 3152

Bright Silver for decorative and technical applications

Heaters

Quartz, titanium, PTFE or PVDF immersion heaters are


recommended in conjunction with a suitable thermostat and
safety cut-out.

Electrical Supply

12 V DC power source, providing smoothed current output


and stepless control. A voltmeter and Ampere-minute meter
should also be included.

3. Working Parameters
pH

14 ( 13 14)

Current density (typical values)

0.5 - 1.2 A/dm for rack operation


0.2 - 0.4 A/dm for barrel operation

Bath voltage

Approx. 1 V, increasing to 4 V if larger anode to cathode


distances are used.

4. Make-Up
Make-Up of 100 lt

Rack Operation

Barrel Operation

Potassium Silver Cyanide (54% Ag)

5.5 kg

3.7 kg

Potassium Cyanide (sodiumfree)

10.0 kg

10.0 kg

5.0 kg (0.4 l)

5.0 kg (0.4 l)

(2.0 kg)

(2.0 kg)

Silverlume A PLUS

0.12 kg (0.12 l)

0.12 kg (0.12 l)

Silverlume B PLUS

0.325 kg (0.325 l)

0.325 kg (0.325 l)

EXPT Silbertrisalyt Base


EXPT Silbertrisalyt Conductive Salt

Note: Pre-cleaning of existing and preparation of new equipment is covered separately.


Examine the plating cell, filter unit and pipework for any signs of leaking, then mark or use a dipstick to identify the final volume level (with pump on).

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Bright Silver for decorative and technical applications

5. Make-Up Sequence
The following sequence refers to equipment which has been prepared, rinsed with DI-Water and drained.
1.) Add approximately half of the required amount of DI-Water to the tank/ sump.
2.) Switch on the extraction and carefully add the required quantity of Potassium Cyanide and EXPT
Silbertrisalyt Conductive Salt, and mix well.
3.) Carefully add the required quantity of Potassium Silver Cyanide (54% Ag) and EXPT Silbertrisalyt
Base, and mix well to completely dissolve.

Optional stages - recommended for improved quality work and trouble-free operation:
3.a)

Either circulate through a carbon pack filter cartridge or batch carbon treat overnight in a
separate tank (using 0.5 1.0 g/l of activated carbon powder).

3.b)

Remove carbon filter or filter the electrolyte from the treatment tank into the production unit,
replacing filter with normal pre-rinsed polypropylene filter. Confirm effective treatment by 0.2 A,
10 min Hull cell if possible (uniform matt panel confirms the absence of any organic
contamination).

4.)

Switch on filter pump and solution agitation system (if used) and circulate for at least 30 minutes.
Heating, if required, should be switched on at this stage.

5.)

Add the required quantities of Silverlume A PLUS and Silverlume B PLUS and mix very well,
preferably for several hours.

6.)

Remove a small sample (500 ml) for day-1 analysis (this will also serve later as a performance
standard).

7.)

The Silverlume PLUS solution is now ready for use.

When working with the high-performance Silverlume PLUS the regulations concerning the handling
of cyanide solutions must be observed.

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Bright Silver for decorative and technical applications

6. Operating Conditions
Optimum (Range)
Silver concentration (g/l)

(rack)
(barrel)

30 (20 40)
20 (10 30)

Free Potassium Cyanide (g/l)

100 (75 150)

Temperature (C)

20 (18 25)
Higher temperature reduce throwing power of the
brightness.

Cathode current density (A/dm)

(rack)

1.0 (0.5 2.0)

(barrel)

0.3 (0.2 0.4)

(rack)
(barrel)

67 mg/Amin (100 %)
1 micron in 1.6 min at 1 A/dm
1 micron in 5.33 min at 0.3 A/dm

Deposition rate (all CDs)

Agitation

Filter pump and cathode or barrel movement

7. Maintenance
For every 10,000 Ah (equivalent to 40 kg of deposited silver) add the following:
kg
Silverlume A Plus
Silverlume B Plus

2.0 2.5
0.4 0.8

Ideally these additions should be made (with sufficient agitation) at the end of daily production and/ or after
10 % of Silverlume A PLUS has been consumed.

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Bright Silver for decorative and technical applications

8. Process Control
Potassium Cyanide
In normal use, using an adequate surface area of soluble silver anode, the concentration of both the Silver
and free Potassium Cyanide should remain constant.
However in cases of high drag-out or insufficient anode area, small corrective additions may be required,
based on analysis.
To raise the free Potassium Cyanide level, high purity grade Potassium Cyanide (sodium-free) should be
used (note: large additions will result in solution cooling due to the endothermic dissolution of Potassium
Cyanide).
In the extreme situation where a large addition of Potassium Cyanide is required, the Potassium Cyanide
should be separately dissolved in a portion of the electrolyte, allowed to stand for a few hours and then
filtered prior to returning to the original solution.
In cases where the free Potassium Cyanide level exceeds the maximum limit (usually when inert anodes are
used), an addition of Potassium Silver Cyanide (80.5% w/w Ag), followed by dilution, should help to reduce
the concentration.
Silver
To raise the silver metal concentration by 1 g/l, add 1.85 g/l Potassium Silver Cyanide (54% Ag) and
2.0 g/l EXPT Silvertrisalyt Replenisher.
Potassium Carbonate
Silver Cyanide electrolytes are strongly alkaline and as a result of atmospheric carbon dioxide and electrolyte
breakdown, Potassium Carbonate will be formed.
High levels of this by-product will cause a lack of throwing power and cause a reduction in the effective
plating range due to high CD burning. Potassium Carbonate has a very high solubility and hence is only
practically removed by precipitation.
At levels > 100 g/l, it is recommended that the electrolyte is batch treated with the product Decarbonate AG
using the following procedure:

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Silverlume PLUS

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Bright Silver for decorative and technical applications

1. Transfer electrolyte into a treatment tank, preferably fitted with a mechanical stirrer.
2. Heat the solution to approx. 30 C and slowly add the required quantity of Decarbonate AG to the region
of strongest agitation.
3. Mix the electrolyte for 1 hour, then switch off the mixer and allow solution to settle, preferably overnight.
4. Filter the solution back into the production tank, preferably though a finer filter cartridge.
5. The electrolyte is now ready to use.
Calculation:
1 kg of Decarbonate AG will treat 0.78 kg of Potassium Carbonate
For every 100 g/l of Potassium Carbonate to be removed, add 128 g/l Decarbonate AG.
Note: It is only recommended for a maximum of 2x treatments, otherwise a reduced CD range may be
observed.
Silverlume A PLUS
Silverlume A PLUS is the primary organic brightener and requires frequent maintenance. High levels of
Silverlume A PLUS can result in a grainy or streaked appearance. Correction can be made by carbon
purification.
Silverlume B PLUS
Silverlume B PLUS is the essential wetting agent required to maximise the effect of
Silverlume A PLUS over a wide plating range. Excess of Silverlume B PLUS can lead to low CD haziness
and restrict the high CD limit. Correction can be made by carbon purification.

9. Typical deposit characteristics


As-plated deposit
Electrical conductivity
Hardness

Fully aged deposit


1.88 /
cm
110 HV

1.66 / cm
80 HV

10. Use of Inert Anodes


Where possible, soluble anodes should be used, but for some applications, e.g. extreme recesses, inert
anodes may be necessary. For these cases, the cell voltage should be as low as possible, either by
increasing the anode surface area or by using a different material. Too high voltages will cause polymeric
cyanide products to form, resulting in discolouration and eventually residue precipitation. These products
may interfere with the performance of the brightener and may require purification. The use of inert anodes
will also require silver replenishment and an increase in free Potassium Cyanide, resulting in more frequent
maintenance.
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Bright Silver for decorative and technical applications

11. Pre-treatment Recommendations


Copper and alloy components require simple cleaning and activation prior to silver plating. However,
substrate containing lead, tin, zinc or iron must be pre-plated with cyanide copper prior to applying a silver
deposit.

10. Silver Strike


Equipment
Tanks

PVC, or sheet steel with hard rubber lining, tanks of selfsupporting PVC or polyethylene

Anodes

Stainless steel (typically 18 Cr Ni 8)

Bath voltage

For rack plating : 3 - 4 V


For barrel plating: 3 - 8 V

Duration of silver strike

3 - 20 s with component movement.


Rack: to maximum 10 s. Barrel: to maximum 30 s
Silver struck components are then transferred to the
Silverlume Plus electrolyte without rinsing.

Make-Up
Make-up of 100 l

Liter

kg

0.2

0.28
0.25
10.0

Potassium silver cyanide (54% Ag)


EXPT Silber-Trisalyt Base
Potassium cyanide (sodium-free)
Distilled water should be used for making up silver baths.

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Bright Silver for decorative and technical applications

Maintenance
The silver concentration needs to be maintained within the range 1 - 3 g/l. when required by the addition of
Potassium Silver Cyanide (54% Ag). Adhesion concerns may occur if the silver concentration falls below 1 g/l
or exceeds 3 g/l.
The performance of the silver strike can be confirmed by simple immersion (without current) of a precleaned/ acid activated copper or brass test panel. A minimum duration of 15 s prior to immersion coating
indicates satisfactory condition of the silver strike. Less than 15 s indicates the need to increase the free
cyanide content until a pass is achieved.

12. Post-Treatment
Certain substrates (with pores or other inhomogenities), may cause surface spots or blooms to form (due to
entrapment of electrolyte residues) after silver-plating. To prevent this situation occurring, it is recommended
to immerse the rinsed articles in 3 %w/w acetic acid post dip with further thorough rinsing.

13. SAP No. for Make - Up and Maintenance Products


PRODUCT

SAP No.

EXPT SILBER TRISALYT BASE


EXPT SILBER TRISALYT REPLENISHER
EXPT SILBER TRISALYT CONDUCTIVE SALT
SILVERLUME A PLUS
SILVERLUME B PLUS
DECARBONATE AG

1687428
1685787
1685788
1683400
1682998
1684950

14. General Safety Precautions


Avoid direct contact with this material. Do not inhale associated mist or vapors. Wash contaminated clothing
before reuse. Refer to Material Safety Data Sheet (MSDS) for specific precautions before handling this
material and for first aid recommendations. As applicable, keep exposure below the limits recommended by
the appropriate regional regulatory agencies.
For further information regarding safe handling of the product please refer to the
corresponding MSDS. The MSDS is provided as part of the ordering process. If you
don't have a copy of the MSDS for a product then it can be obtained, on request,
from the appropriate regional Atotech office.

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Silverlume PLUS

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Bright Silver for decorative and technical applications

15. Recommendations for Wastewater Treatment


Rinse waters and concentrates of Silverlume PLUS must always be subjected to special treatment due to
the containing cyanide and possible complexing agents.
Rinse Water
The rinsing steps after silver plating should be designed in such a manner that the dragged-out silver can be
effectively recovered by suitable recycling techniques. A strong alkaline ion exchanger (e.g. Lewatit
MonoPlus M 500) can be used for this purpose at a concentration of maximum 2 mval Ag/l.
Once all the silver has been removed from the rinse water, it may be directly sent to the final neutralization
process.
The ion-exchanger resin which has become loaded with silver can be sent to a special company for recovery
of the silver.
If there is cyanide which is easily releasable, a cyanide oxidation has to be carried out supplementary.
If no recovery system exists on the drag-out rinse after using Silverlume PLUS, the containing cyanide has
to be treated first by an oxidation followed by a heavy metal precipitation.
The heavy metals can be precipitated either by a neutralization precipitation at pH 10 - 11 or using sodium
sulfide at pH 6 - 8.
Add sodium sulphide solution (10 15 %) until a significant potential jump can be recognized during a
potentiometric measurement or until lead acetate paper shows a brown colour. After a reaction time of
10 min remove the weak sulphide excess with a small amount of iron-III-chloride solution (about 10 %).
The lead acetate paper should no longer be brown in colour.
Then adjust the pH to 9 with caustic soda/calcium hydroxide.
For better flocculation add flocculation agent (we recommend polyacryl amide/anionic with a mol mass of
4 6 million) and stir. Allow the precipitate to settle for better filtration over a special filter press.
After filtration is complete the filtrate must not be mixed with metal ions bearing waste streams.The filtrate
must be sent to the final neutralization process, bypassing the waste water treatment plant.

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Bright Silver for decorative and technical applications

Concentrates
When silver is to be recycled, it is generally necessary to treat these silver solutions separately from other
solutions.
The following recycling methods are typical, although others can be recommended:

Electrowinning of silver using an appropriated electrolytic cell, followed by an oxidation of the remaining
cyanide.
Treatment of silver concentrate, or of a precipitated silver sludge, by a specialized recycling company.

If these methods cannot be used, the silver concentrate must be diluted in a ratio of 1 : 10 before sending to
the waste water treatment plant. This treatment is carried out as described above.

Be sure to observe all local regulations concerning the limit values of pollutants
including the general regulations on dangerous materials!!

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Bright Silver for decorative and technical applications

16. Analytical Instructions


Version: 01

Silverlume B Plus by LC

Doc.-No.: A0002280-01

Principle:
Reversed Phase High Efficiency Liquid Chromatography (HPLC) using UV-detection and external standards
Reagents required:
Silverlume B Plus, 1000 ml/l reference material
Phosphoric acid 85 %, HPLC quality
Acetonitrile HPLC-MS quality
De-ionized water (Millipore quality)

Please follow the general regulations for hazardous materials in the Material safety
data sheets!
The analytical procedure is to be followed exactly.
Be sure to observe all local regulations concerning the permitted limits for
pollutants.

Equipment required:
HPLC-system with manual or automatic sampling UV-detector, data processing- or
integration system
Standard laboratory equipment

The aforesaid listed equipment is only valid when this method has been created.
For purchase of new analytical equipment the recommend equipment list has to be followed:
https://10.187.127.52/Communication/html/scientific_services_chemical_services_analytics.php

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Bright Silver for decorative and technical applications

Procedure:
Operating Parameter:
Operation Mode isocratic
Eluent A
0.1 % H3PO4 in de-ionized water (Millipore quality)
(1.0 mL 85 % phosphoric acid in 1000 mL de-ionized water)
Eluent B
Acetonitrile
Time
0.0
3.0

Flow
1.5
1.5

A [%]
80
80

B [%]
20
20

Flowrate
1.5 mL/min
Analytical Column
Purospher Star RP-18 endcapped from Merck, 55 x 4 mm, 3 m
Runtime
3 min
Injection volume 5 L,
Ext. temperature:
25 C
Detection
UV/VIS at = 254 nm
Pressure
approx. 1500 - 2000 psi
Evaluation
Waters Millenium 32 V 3.05.01
Standard solutions:
Silverlume B Plus stock solution:
Pipette 0.5 mL** of Silverlume B Plus in a 100 mL volumetric flask and fill up with de-ionized to the
calibration mark. This corresponds to a concentration of 5 mL/L.
Standard Solutions:
Standard solutions with the following concentrations in water are prepared out of the stock solutions:
0.05 mL/L, 0.1 mL/L and 0.5 mL/L*
*The correct values have to be calculated out of the real initial weight and the content of Silverlume B Plus in
the certified reference.
Sample Preparation
Depending on the contents the sample is diluted with de-ionized water in a way that the measured peak
areas are within the calibration curve e.g. 1:20 or 1:10.

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Silverlume PLUS

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Bright Silver for decorative and technical applications

Evaluation:
Retention time:

Silverlume B Plus
approx. 1.0 min

The content of Silverlume B Plus is evaluated via linear external calibration. The content in mL/L is
calculated as follows.

Content Silverlume B Plus mL/L = content

Silverlume B Plus

mL/L dilution factor

Example:
Fig.1: Example chromatogram of a sample solution diluted 1:10.
0,110

0,100

0,090

0,080

0,070

AU

0,060

0,050

0,040

0,030

0,986

0,020

0,010

0,000
0,20

0,40

0,60

0,80

1,00

1,20

1,40
1,60
Minutes

1,80

2,00

2,20

2,40

2,60

2,80

3,00

Quality assurance: For maintenance, calibration of measuring devices


and the use of standards and reference materials please refer to the
corresponding guidelines.

*
Unless otherwise stated, these are always analytical grade substances.
** Volumes given exact to a decimal point must be measured with a volumetric pipette.
*** For the purpose of calculation, the factor of the standard solution is assumed to be 1.000 and is
therefore not taken into account in the examples.

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Bright Silver for decorative and technical applications

Determination of Carbonate by Titration of the Precipitated


Barium Carbonate

Version: 01
Doc.-No.: EXT-0344-TIT-01

Reagents required*:

Ammonium chloride
Ammonia conc. (density 0.91)
Barium chloride solution 1 M (244 g/l BaCl2 2 H2O)

Methylorange indicator solution 0.1 %


Hydrochloric acid volumetric solution 0.5 N

Be sure to observe all local regulations concerning the permitted limits for
pollutants, including the general regulations for hazardous materials!

Procedure:

10.0 ml** bath are allowed to run into a 250 ml glass beaker,
2 g solid ammonium chloride,
2 ml ammoniac conc. and
100 ml distilled water added to it and the solution heated almost to boiling point.
20 ml 1 m barium chloride solution are then added to it while stirring well. After the precipitate has
settled, the solution is filtered while still hot and the precipitate washed out well with hot distilled water
(about three to five times) until the flowing filtrate no longer turns red litmus paper blue. The washed-out
filter with precipitate on it is then returned to the precipitation beaker and about 100 ml hot distilled
water and
2 - 3 drops methylorange indicator solution added to it. Titration is then performed against
0.5 N hydrochloric acid volumetric solution until the yellow solution turns red and no longer turns yellow
again even after 1 - 2 minutes have passed.

The number of ml 0.5 n hydrochloric acid volumetric solution used***

multiplied by 2.65 produces the sodium carbonate content of the bath


multiplied by 3.45 produces the potassium carbonate content of the bath in g/l

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Example:
The following amount was used for the titration of 10.0 ml bath:
15.2 ml 0.5 n hydrochloric acid volumetric solution
Calculation:
15.2 x 2.65 = 40.3 g/l sodium carbonate
15.2 x 3.45 = 52.4 g/l potassium carbonate

*
Unless otherwise stated, these are always analytical grade substances.
** Volumes given exact to a decimal point must be measured with a volumetric pipette.
*** For the purpose of calculation, the factor of the standard solution is assumed to be 1.000 and is
therefore not taken into account in the examples.

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Bright Silver for decorative and technical applications

Version: 01

Determination of Carbonate by Direct Titration

Doc.-No.: EXT- 0345-TIT-01

Reagents required*:

Sodium chloride
Silver nitrate solution 1 N (170 g/l AgNO3)

Phenolphthalein indicator solution, 1 % in alcohol


Hydrochloric acid volumetric solution 0.5 N

Be sure to observe all local regulations concerning the permitted limits for
pollutants, including the general regulations for hazardous materials!

Procedure:

10.0 ml** bath are diluted in a 300 ml Erlenmeyer flask with


100 ml distilled water. After the addition of
2 g solid sodium chloride, somewhat more than a fifth of
1 n silver nitrate solution of that amount of
0.1 N silver nitrate volumetric solution which was used for the cyanide titration with a
5.0 ml bath sample is added while shaking vigorously.

If, for example, 14.5 ml 0.1 n silver nitrate volumetric solution were used in a matt silver bath
(5.0 ml bath sample), then 14.5 : 5 = about 3 ml 1 n silver nitrate solution should be added.
If 24.2 ml 0.1 n silver nitrate volumetric solution were used in a bright- silver bath
(2.5 ml bath sample), then (24.2 x 2) : 5 = about 10 ml 1 n silver nitrate solution should be added.
After this, a few drops of phenolphthalein indicator solution are added and titration performed against 0.5 n
hydrochloric acid volumetric solution until the red solution becomes completely colorless.
The number ml 0.5 n hydrochloric acid volumetric solution used***

multiplied by 5.3 produces the sodium carbonate content of the bath


multiplied by 6.9 produces the potassium carbonate content of the bath in g/l.

Example:
The following amount was used for the titration of 10.0 ml bath:
7.6 ml 0.5 n hydrochloric acid volumetric solution
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Bright Silver for decorative and technical applications

Calculation:
7.6 x 5.3 = 40.3 g/l sodium carbonate
7.6 x 6.9 = 52.4 g/l potassium carbonate
Remarks:
If a bath contains hydroxide (the pH value is then higher than 12.0), the hydroxide must be titrated in a
second sample, to which 20 ml of a 1 m barium chloride solution (244 g/l BaCl 2 H O) are added in
2

addition to the above-stated amounts of sodium chloride, 1 n silver nitrate solution and phenolphthalein
indicator solution. The ml 0.5 n hydrochloric acid volumetric solution used for this process are to be
subtracted from the first titration result.
Example:
The following amount was used for titration without the addition of 1 m barium chloride solution:
12.6 ml 0.5 n hydrochloric acid volumetric solution
The following amount was used for titration after the addition of 1 m barium chloride solution:
5.0 ml 0.5 n hydrochloric acid volumetric solution
Calculation:

12.6 ml 0.5 n hydrochloric acid volumetric solution = amount used for carbonate + hydroxide
5.0 ml 0.5 n hydrochloric acid volumetric solution = amount used for hydroxide
7.6 ml 0.5 n hydrochloric acid volumetric solution = amount used for carbonate

7.6 x 5.3 = 40.3 g/l sodium carbonate


7.6 x 6.9 = 52.4 g/l potassium carbonate

*
Unless otherwise stated, these are always analytical grade substances.
** Volumes given exact to a decimal point must be measured with a volumetric pipette.
*** For the purpose of calculation, the factor of the standard solution is assumed to be 1.000 and is
therefore not taken into account in the examples.

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Bright Silver for decorative and technical applications

Version: 02

Determination of the Content of Free Cyanide by Titration

Doc.-No.: EXT-0001-TIT-02

Principle:
Redox titration
Required reagents*:

Ammonia solution 5 N (375 ml/l ammonia conc., density 0.91)


Potassium iodide solution 1 M (166 g/l potassium iodide)
Silver nitrate volumetric solution 0.1 N

Be sure to observe all local regulations concerning the permitted limits for
pollutants, including the general regulations for hazardous materials!

Procedure:

5.0 ml** bath in the case of matt-silver baths


2.5 ml** bath in the case of bright-silver and flash-silver baths

(10.0 ml** bath are poured into a 100 ml graduated flask, which is then filled up to the mark with distilled
water. After mixing well 50.0 ml** = 5.0 ml or 25.0 ml** = 2.5 ml original bath are removed from the flask.)
The bath sample is diluted in a

300 ml Erlenmeyer flask with


100 ml DI water and mixed with
5 ml of 1 M Potassium iodide solution and
5 ml of 5 N Ammonia solution. Titration with
0.1 N Silver nitrate volumetric solution is then performed until the precipitate which forms on entry of the
drops no longer resolves after being shaken several times, but causes general turbidity of the solution.

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Version: 09

Silverlume PLUS

Doc.-No.: 3152

Bright Silver for decorative and technical applications

The volume in ml of the 0.1 M Silver nitrate standard solution*** used for the titration of 5 ml sample,

multiplied by 1.96, gives the content of free Sodium cyanide in g/l.


multiplied by 2.60, gives the content of free Potassium cyanide in g/l.

The volume in ml of the 0.1 M Silver nitrate standard solution*** used for the titration of 2.5 ml sample,

multiplied by 3.92, gives the content of free Sodium cyanide in g/l.


multiplied by 5.20, gives the content of free Potassium cyanide in g/l.

Examples:
a) The following amount was used for the titration of 5.0 ml bath:
14.5 ml of 0.1 N Silver nitrate volumetric solution
Calculation:
14.5 x 1.96 = 28.4 g/l free Sodium cyanide
14.5 x 2.60 = 37.7 g/l free Potassium cyanide
b) The following amount was used for the titration of 2.5 ml bath:
24.2 ml of 0.1 N Silver nitrate volumetric solution
Calculation:
24.2 x 3.92 = 94.9 g/l free Sodium cyanide
24.2 x 5.20 = 125.8 g/l free Potassium cyanide

*
Unless otherwise stated, these are always analytical grade substances.
** Volumes given exact to a decimal point must be measured with a volumetric pipette.
*** For the purpose of calculation, the factor of the standard solution is assumed to be 1.000 and is
therefore not taken into account in the examples.

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Version: 09

Silverlume PLUS

Doc.-No.: 3152

Bright Silver for decorative and technical applications

Version: 01

Silver in cyanidic silver baths by F-AAS

Doc.-No.: A0002247-01

Principle:
The silver-containing sample is diffused and atomized in a compression air/acetylene-flame and the
absorption is measured at a wavelength of 328.1 nm. The determination is carried out through external
calibration by using corresponding standard solutions.
Reagents required:
Nitric Acid (HNO3), conc. (65 %), e.g. by Merck
Silver standard solution: 1000 mg/l
DI water

Please follow the general regulations for hazardous materials in the Material safety
data sheets!
The analytical procedure is to be followed exactly.
Be sure to observe all local regulations concerning the permitted limits for
pollutants.

Equipment required:
Atomic Absorption Spectrometer with control and evaluation unit (e.g. Perkin Elmer, Varian)
Burner: Air/Acetylene one-slit burner head
Hollow cathode lamp: Silver

Operating mode

Absorption

Gas mixture

Compression air/acetylene

Lamp current

8 mA

Fuel flow

2.0 L/min

Integration time

1.0 s

Oxidant flow

13.5 L/min

Replicates

Wavelength

328.1 nm

Background correction

OFF

Slit

0.5 nm

Delay

30 sec

Calibration

New Rational

Rinse time

25 s

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Doc.-No.: 3152

Bright Silver for decorative and technical applications

The aforesaid listed equipment is only valid when this method has been created.
For purchase of new analytical equipment the recommend equipment list has to be followed:
https://10.187.127.52/Communication/html/scientific_services_chemical_services_analytics.php

Procedure:
Calibration procedure:
0.5 mg/l Ag: 50 L of silver standard solution and 2 ml of nitric acid are pipetted into a 100 mlflask then
filled up to the mark with DI water and homogenized.
1 mg/l Ag:

100 L of silver standard solution and 2 ml nitric acid are pipetted into a 100 ml flask then filled
up to the mark with DI water and homogenized.

2 mg/l Ag:

200 L of silver standard solution and 2 ml of nitric acid are pipetted in to a 100 ml flask then
filled up to the mark with DI water and homogenized.

Sample preparation:
IMPORTANT NOTE:
The substance contains cyanide which on contact with acids will produce
hydrocyanic acid gas (HCN).
All operations have to be carried out under the fume cupboard!

1.0 ml** and 0.5 ml** of sample are pipetted into a 100 ml volumetric flask (dilution: 1:100/1:200)
Prior to analysis the sample hast to be further diluted (1:100):
1 ml** of each pre-diluted sample (1:100/1:200) is pipetted into a 100 ml volumetric flask.
Add 50 ml of deionized water and then (carefully!!!) add 4.0 ml of nitric acid.
After that the flask is filled up to the mark with deionized water.
the homogenized solution is analyzed at a wavelength of 328.1 nm

Evaluation:
The determination of the Ag content in the diluted sample is carried out automatically through the PCsoftware via the external calibration, which was carried out before. The determined silver concentration C Ag
[mg/l] for the diluted sample must be multiplied with the dilution factor. The determined silver content must be
within the calibration curve, otherwise another dilution has to be chosen.
CAg [mg/l] dilution factor = mg/l of Ag in the sample.

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Doc.-No.: 3152

Bright Silver for decorative and technical applications

Example:
1.13 mg/l 10000 = 11.3 g/l of silver

Quality assurance: For maintenance, calibration of measuring devices


and the use of standards and reference materials please refer to the
corresponding guidelines.

*
**

Unless otherwise stated, these are always analytical grade substances.


Volumes given exact to a decimal point must be measured with a volumetric pipette.

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Version: 09

Silverlume PLUS

Doc.-No.: 3152

Bright Silver for decorative and technical applications

Determination of Silver with Ammonium Thiocyanate by


Titration

Version: 03
Doc.-No.: EXT-0346-TIT-03

Reagents required*:

sulfuric acid conc. (density 1.84)


nitric acid conc. (density 1.40)
Iron(III)-ammonium sulphate solution 0.4 M (19.3 g NH 4Fe(SO4)2 x 12 H2O + 10 ml H2SO4 5M topped
up to 100 ml with distilled water)
Ammonium thiocyanate volumetric solution 0.1 M

Please follow the general regulations for hazardous materials in the Material safety
data sheets!
The analytical procedure is to be followed exactly.
Be sure to observe all local regulations concerning the permitted limits for
pollutants.
Procedure:

2.5 ml** silver bath are transferred into a 250 ml Erlenmeyer flask. After the addition of
10 ml distilled water,
3 ml of the sulphuric acid and 4.5 ml nitric acid added carefully.

IMPORTANT NOTE:
The substance contains cyanide which on contact with acids will produce hydrocyanic acid
gas (HCN) All operations have to be carried out under the fume cupboard!

Heat the flasks until all the deposit have disappeared and the solution has boiled for
5 - 10 minutes. After cooling down it is diluted with
90 ml distilled water. After the addition of
1.0 ml 0.4 M iron(III)-ammonium sulphate solution. Titration is performed against
0.1 M Ammonium thiocyanate volumetric solution until the whitish turbid solution turns bright-red/brown.

Alternative: The Titration can be conducted as a turning point titration


using a titroprocessor equipped with a platinium electrode to
determine the first endpoint.

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Doc.-No.: 3152

Bright Silver for decorative and technical applications

Evaluation:
The number of ml 0.1 M Ammonium thiocyanate volumetric solution used *** multiplied by 4.315 produces the
silver content of the bath in g/l.
Example:
The following amount was used for the titration of 2.5 ml silver bath:
7.84 ml 0.1 N ammonium thiocyanate volumetric solution***
7.84 x 4.315 = 33.8 g/l silver

Quality assurance: For maintenance, calibration of measuring devices


and the use of standards and reference materials please refer to the
corresponding guidelines.

Unless otherwise stated, these are always analytical grade substances.


given exact to a decimal point must be measured with a volumetric pipette.
***
For the purpose of calculation, the factor of the standard solutions is assumed to be
1.000 and is therefore not taken into account in the examples.
** Volumes

This sheet shall serve for your information. The content of the sheet is based on our best
knowledge. We do not undertake any duty to advise. The contents of the sheet shall not
be considered as an agreement on condition and quality of the goods delivered.
The decision to use our products for its production purposes is the responsibility of our
customer. We can accept liability only for the quality of our products at delivery. If
difficulties arise in the application of our products, we propose that you contact our
technical service department.

Atotech Deutschland GmbH


P.O. Box: 21 07 80
10507 Berlin, Germany
Erasmusstrae 20
10553 Berlin, Germany
phone +49 (0) 30 349 85 0
fax +49 (0) 30 349 85 777

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Version: 09

Silverlume PLUS

Doc.-No.: 3152

Bright Silver for decorative and technical applications

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