BRITISH STANDARD BS 3727-15:

1968

Methods for
Licensed copy: I P, The University of Leeds, Version correct as of 08/04/2013 09:07, (c) The British Standards Institution 2013

The analysis of nickel

for use in electronic
tubes and valves —
Part 15: Determination of Zinc
(Photometric Method)
 BS 3727-15:1968
Licensed copy: I P, The University of Leeds, Version correct as of 08/04/2013 09:07, (c) The British Standards Institution 2013
This British Standard, having
been approved by the
Telecommunications Industry
Standards Committee and
endorsed by the Chairman of
the Engineering Divisional
Council, was published
under the authority of
the General Council on
26 January 1968
© BSI 12-1999
The following BSI references
relate to the work on this
standard:
Committee references TLE/5,
TLE/5/3 and TLE/5/3/1
Draft for comment 66/17440
ISBN 0 580 00043 5
Co-operating organizations
The Telecommunication Industry Standards Committee, under whose
supervision this British Standard was prepared, consists of representatives
from the following Government departments and scientific and industrial
organizations:
British Broadcasting Corporation
British Electrical and Allied Manufacturers’ Association
British Radio Equipment Manufacturers’ Association
British Radio Valve Manufacturers’ Association*
British Railways Board
Cable and Wireless Ltd.
Crown Agents for Oversea Governments and Administrations
Electrical Contractors’ Association (Incorporated)
Electrical Research Association
Electricity Council, the Central Electricity Generating Board and the Area
Boards in England and Wales
Electronic Engineering Association*
Electronic Valve and Semiconductor Manufacturers’ Association*
Institution of Electrical Engineers
Institution of Electronic and Radio Engineers*
Institution of Production Engineers
Ministry of Defence
Ministry of Defence, Army Department
Ministry of Defence, Navy Department*
Ministry of Labour (H.M. Factory Inspectorate)
Ministry of Technology*
Post Office*
Radio & Electronic Component Manufacturers’ Federation
Relay Services Association of Great Britain
Science Research Council — Radio and Space Research Station
Telecommunication Engineering and Manufacturing Association
The Government departments and scientific and industrial organizations
marked with an asterisk in the above list, together with the following, were
directly represented on the committees entrusted with the preparation of this
standard:
Scientific Instrument Manufacturers’ Association
United Kingdom Atomic Energy Authority
Manufacturers of nickel alloys
Amendments issued since publication
Amd. No. Date Comments
 BS 3727-15:1968

Contents

Page
Co-operating organizations Inside front cover
Foreword ii
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1 Introduction 1
2 Apparatus 1
3 Reagents required 1
4 Sampling 1
5 Calibration 1
6 Procedure 2

© BSI 12-1999 i
 BS 3727-15:1968

Foreword

This standard makes reference to the following British Standards:

BS 1499, Sampling non-ferrous metals.
This method for the determination of zinc is the fifteenth of a series of methods
Licensed copy: I P, The University of Leeds, Version correct as of 08/04/2013 09:07, (c) The British Standards Institution 2013

which will form a complete British Standard under the collective title “Analysis
of nickel for use in electronic tubes and valves”, each method being published as a
separate part. Other parts in the series are as follows:
— Part 1: Aluminium;
— Part 2: Boron;
— Part 3: Carbon;
— Part 4: Chromium;
— Part 5: Cobalt;
— Part 6: Copper;
— Part 7: Iron;
— Part 8: Manganese;
— Part 9: Magnesium;
— Part 10: Silicon 0.020–0.25 per cent;
— Part 11: Silicon 0.001–0.020 per cent;
— Part 12: Sulphur1);
— Part 13: Titanium;
— Part 14: Tungsten;
— Part 16: Combined and free magnesium;
— Part 17: Not yet allocated;
— Part 18: Not yet allocated;
— Part 19: Not yet allocated;
— Part 20: Spectrographic method;
— Part 21: Magnesium (atomic absorption);
— Part 22: Zinc (atomic absorption).
These methods have been found to give reliable and reproducible results and are
primarily intended as reference methods to be used in cases of dispute.
A British Standard does not purport to include all the necessary provisions of a
contract. Users of British Standards are responsible for their correct application.

Compliance with a British Standard does not of itself confer immunity

from legal obligations.

Summary of pages
This document comprises a front cover, an inside front cover, pages i and ii,
pages 1 and 2 and a back cover.
This standard has been updated (see copyright date) and may have had
amendments incorporated. This will be indicated in the amendment table on the
inside front cover.

1)
In course of preparation.

ii © BSI 12-1999
 BS 3727-15:1968

1 Introduction 3 Reagents required

1.1 Principle. A hydrochloric acid solution of the All reagents shall be of suitable purity2), distilled
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sample is prepared and after reduction of iron to the water shall be used throughout and the solutions
ferrous state, the chlorozinc complex is extracted shall be freshly prepared.
with di-n-octylmethylamine into xylene. After Standard zinc solution. Dissolve 125 mg of pure
rejection of the aqueous phase containing the nickel zinc in hydrochloric acid (d = 1.16–1.18) and dilute
and most of the heavy metals, the zinc is to 1 litre with water. Pipette 10.0 ml of this solution
back-extracted into an alkaline solution. After into a 500 ml volumetric flask, dilute to the mark
addition of bis-cyclohexanone oxalyldihydrazone to with water and mix (1 ml contains 2.5 Èg zinc).
complex traces of copper, the zinc is extracted into
Nitric acid (50 % v/v). Dilute 500 ml of nitric acid
chloroform as its complex
(d = 1.42) to 1 litre with water.
with 1-(2-pyridylazo)-2-naphthol. The optical
density of the final solution is measured at 560 mÈ. Hydrochloric acid (concentrated), d = 1.16–1.18.
Only cadmium would interfere in the method, but is Hydrochloric acid (50 % v/v). Dilute 500 ml of
absent in nickel used for electronic tubes and valves. hydrochloric acid (d = 1.16–1.18) to 1 litre with
1.2 Range. 0.0005 % to 0.03 % zinc (by adjustment water.
of sample weight). Hydrochloric acid (25 % v/v). Dilute 250 ml of
1.3 Reproducibility. Experiments have been hydrochloric acid (d = 1.16–1.18) to 1 litre with
carried out independently by a number of analysts water.
using the method recommended in this standard. Ascorbic acid. Solid.
The degree of reproducibility that can be expected is Di-n-octylmethylamine solution (5 % v/v).
shown by the following analysis of the results Dilute 10 ml di-n-octylmethylamine to 200 ml with
obtained: xylene.
Zinc content Standard deviation Potassium hydroxide solution (4 % w/v).
0.001 % 0.0001 Dissolve 40 g of potassium hydroxide in 1 litre of
0.01 % 0.001 water.
Ammonium chloride solution (5 % w/v).
1.4 Application. This method is applicable to Dissolve 50 g of ammonium chloride in 1 litre of
nickel primarily intended for use in electronic water.
devices. Such nickel contains not more than:
Bis-cyclohexanone oxalyldihydrazone (0.1 % w/v).
Aluminium 0.1 % Dissolve 0.1 g of bis-cyclohexanone
Chromium 0.03 % oxalyldihydrazone in 100 ml of methanol.
Cobalt 1% 1-(2-pyridylazo)-2-naphthol (0.1 w/v). Dissolve 0.1 g
Copper 0.2 % of 1-(2-pyridylazo)-2-naphthol in 100 ml of
methanol.
Iron 0.25 %
Chloroform
Manganese 0.25 %
Magnesium 0.15 % Sodium sulphate (anhydrous). Solid.
Silicon 0.25 % 4 Sampling
Titanium 0.03 %
Recommended methods of obtaining a suitable
Tungsten 5% sample for the analytical procedure given are
described in BS 14993).
2 Apparatus
2.1 Class A volumetric glassware shall be used 5 Calibration
throughout, complying with the relevant 5.1 Make additions of the standard zinc solution to
British Standard. six separating funnels as follows:
2.2 Any instrument suitable for measuring the 0, 1.0, 2.0, 4.0, 6.0, 8.0 ml.
optical density of the solution at a wavelength
of 560 mÈ may be used.

2) Analytical grade reagents have been found suitable.

3) BS 1499, “Sampling non-ferrous metals”.

© BSI 12-1999 1
 BS 3727-15:1968
Dilute each to 10 ml with water and add 10.0 ml of
hydrochloric acid (50 % v/v). Add 75 mg of ascorbic
acid, mix and add 10.0 ml of di-n-octylmethylamine
Licensed copy: I P, The University of Leeds, Version correct as of 08/04/2013 09:07, (c) The British Standards Institution 2013
solution (5 % v/v).
5.2 Shake for 1 minute, allow to separate and reject
the lower aqueous layer. Add 10.0 ml of
hydrochloric acid (25 % v/v), shake for 1 minute,
allow to separate and reject the lower aqueous layer.
Repeat this washing with 10.0 ml of hydrochloric
acid (25 % v/v). Discard the lower aqueous layer.
Add 10.0 ml of potassium hydroxide
solution (4 % w/v), shake for 1 minute, allow to
separate and run off the lower aqueous layer into a
clean 100 ml separating funnel. Rinse the original
separating funnel with 10 ml of water and add the
washings to the second separating funnel. Discard
the organic layer. Add 10.0 ml of ammonium
chloride solution (5 % w/v) to the aqueous solution.
Add by pipette 5.0 ml of bis-cyclohexanone
oxalyldihydrazone solution (0.1 % w/v), mix and
allow to stand for 3 minutes. Add by pipette 1.0 ml
of 1-(2-pyridylazo)-2-naphthol solution (0.1 % w/v)
and 10 ml of chloroform. Shake for 1 minute, allow
to separate and run the organic layer into a
dry 25 ml volumetric flask. Repeat the extraction
twice with 5 ml portions of chloroform. Combine the
extracts and dilute to volume with chloroform.
Add 1 g of anhydrous sodium sulphate and mix.
Measure the optical density against chloroform
at 560 mÈ using a 1 cm cell.
Correct the optical density for the blank
(no added zinc), and prepare a calibration graph.
4)
A Whatman No. 44 has been found suitable.
2 © BSI 12-1999
6 Procedure
A blank should be carried through the entire
procedure, omitting the sample.
Weigh 250 mg of sample (Note 1) into a 100 ml
beaker. Dissolve in 2 ml of nitric acid (50 % v/v) and
bake until free from acid. Cool, add 5 ml of
hydrochloric acid (d = 1.16–1.18) and evaporate to
dryness.
Redissolve in 10.0 ml of hydrochloric acid (25 % v/v)
and transfer to a 100 ml separating funnel, rinsing
the beaker with 10.0 ml of hydrochloric
acid (25 % v/v) (Note 2). Add 75 mg of ascorbic acid
(Note 3) mix and add 10.0 ml of
di-n-octylmethylamine solution (5 % v/v) and then
proceed as in 5.2.
Obtain the percentage zinc in the sample by
reference to the calibration graph after correcting
for the blank.
NOTE 1 With 250 mg of sample the upper limit of the method
is about 0.007 %. By taking 50 mg of sample this may be
extended to 0.04 % zinc. Sample weights greater than 250 mg
may be taken.
NOTE 2 Samples containing tungsten can be conveniently
filtered at this stage. Transfer the solution to a separating funnel
through a suitable filter paper4), washing with 10.0 ml of
hydrochloric acid (25 % v/v).
NOTE 3 When the copper content of the 250 mg sample is
known to exceed 0.10 %, it is advantageous to postpone the
addition of ascorbic acid until after the extraction with
di-n-octylmethylamine and the two washings of the organic
phase with hydrochloric acid (25 % v/v). The addition of ascorbic
acid should then be followed by two further washings with
hydrochloric acid (25 % v/v) before back extraction with the
potassium hydroxide solution.
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blank
 BS 3727-15:
1968
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