KENYA STANDARD WHITE SPIRIT—SPECIFICATION

DKS 666:2010

© KEBS 2010 – All Rights Reserved

KENYA STANDARD

WHITE SPIRIT—SPECIFICATION

DKS 666:2010


KENYA BUREAU OF STANDARDS (KEBS)

TECHNICAL COMMITTEE REPRESENTATION The following organizations were represented on the Technical Committee:

University of Nairobi Government Chemist MOR-Materials Dept. Agro Chemical and Food Company Kenyatta University KIRDI Pan Africa Chemicals Ltd Spectre International CIN Associated Battery Manufacturers Marshall Fowler Kenya Bureau of Standards Secretariat

REVISION OF KENYA STANDARDS

In order keep abreast of progress in industry, Kenya standards shall be regularly reviewed. Suggestion for improvements to published standards addressed to the Managing Director, Kenya Bureau of Standards, are welcome.

© Kenya Bureau of Standards, 2010 Copyright. Users are reminded that by virtue of section of the Copyright Act, Cap. 12 of 2001 of the Laws of Kenya, copyright subsists in all Kenya Standards and except as provided under section 26 of this Act, no Kenya Standard produced by Kenya Bureau of Standards may be reproduced, stored in a retrieval system in any form or transmitted by any means without prior permission in writing from the Managing Director.

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KENYA BUREAU OF STANDARDS (KEBS)

Head Office: P.O. Box 54974 Nairobi, Tel.: (+254 02 ) 502211-10, 502543/45, Fax: (+254 02) 503293

E-Mail: [email protected] , Web: http://www.kebs.org Coast Regional Office Western Kenya Region Office R ift valley Regional Office P.O. Box 99376, Mombasa P.O. Box 2949, Kisumu P.O. Box 8111, Eldoret Tel.: (+254 011) 229563, 230939/40 Tel.: (+254 035) 23549, 22396 Tel.: (+254 0321) 3151,63377 Fax: (+254 011) 229448 Fax: (+254 035) 21814 Fax: (+254 0321) 33150

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P R E F A C E This Kenya Standard was prepared by the Technical Committee on Industrial solvents and chemicals under the authority of Kenya Bureau of Standards. During the revision of this standard, the title of the standard changed to ‘White spirit —Specification’. This is because in the market, there has been confusion between turpentine and white spirit. A new method of test for flash point, Pensky-Martens Closed Cup Apparatus has also been introduced to replace setaflash method. During the preparation of this standard, reference was made to the following publications and acknowledgement is made for their assistance with thanks: ASTM D 3120:2008 Standard Test Method for Trace Quantities of Sulphur in Light Liquid Petroleum Hydrocarbons by Oxidative Microcoulometry. ASTM D93-09 Standard Test Methods for Flash Point by Pensky-Martens Closed Cup Tester

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KENYA STANDARD

WHITE SPIRIT- SPECIFICATION

1. Scope and field of application

This Kenya Standard specifies the requirements for white spirit for use in paints, varnishes, lacquers, resins, thinners and cleaning solvents.

2. Required characteristics and their tolerance

White spirit consists essentially of a mixture of hydrocarbons and shall have the requirements shown in Table 1.

3. Sampling

Representative samples, each having a volume of not less than 500 ml, shall be taken in triplicate from one or more original and unopened containers or from the bulk during packaging and shall be packed in clean, dry, airtight containers.The containers shall be of such a size that they are nearly filled by the sample. Each sample container shall be sealed with a material unaffected by the contents.

TABLE 1. REQUIRED CHARACTERISTICS AND THEIR TOLERANCES

SL. NO.

CHARACTERISTIC

REQUIREMENT

METHOD OF TEST

(ii)

Clarity

Clear, no solid matter present

Visual inspection

(ii)

Undissolved water at 20 ± 2oc

Absent

Visual inspection

(iii)

Odour

Free from kerosene smell

Olfactorial

(iv)

Co lour

Not higher than 96.5 lovibond unit

KS 801-10:2004 (using 1 inch cell)

(v)

(a) Initial boiling point (IBP)

150 oC

ANNEX A

(b) Dry point (D.P)

205 oC

(c) Distillation range for 50 per cent distillate

162 oC to 172 oC

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((vi)

Specific gravity (S.G.) 20 ± 2 oC

0.775 to 0.785

ANNEX B

(vii)

Refractive index (R.I.) at 20 ± 2oc

1.434 minimum

ANNEX C

(viii)

Aromatic content

20 per cent (v/v) maximum

ANNEX D

(ix)

Residue on evaporation

5 mg/100 ml

ANNEX E

(x)

Neutrality

When 50 ml of sample is shaken with 19 ml of distilled water, the water layer shall be neutral, to methyl orange

-

(xi)

Sulphur content

5 ppm maximum

ANNEX F

(xii)

Freedom from objectionable sulphur compounds

No more than slight tarnish of copper strip

ANNEX G

(xiii)

Flash point

40 oC minimum

ANNEX H

(xiv)

Evaporation rate

88 ± 10 seconds

ANNEX I

4. Marking and packaging

The solvent shall be packed in a suitable container and marked indelibly with the following information: (i) Manufacturer’s name and /or registered trade mark.

(ii) Net content.

(iii) The name ‘white spirit (mineral turpentine)’.

(iv) ‘Inflammable’ plus the international symbol.

(v) Highly poisonous

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ANNEX A Distillation range A.1 Definitions A.1.1 Initial boiling point — The temperature indicated by the distillation thermometer at the

instant the first drop of condensate leave the condenser tube. A.1.2 Dry point — The temperature indicated at the instant the last drop of liquid evaporates

from the lowest point in the distillation flask, disregarding any liquid on the side of the flask.

A.2 Summary of the method — A 100 ml specimen is distilled under conditions equivalent

to a simple batch differential distillation. The temperature of the mercury in the thermometer is equilibrated with that of the refluxing liquid before the distillate is taken over. Boiling temperatures observed on a partial immersion thermometer are corrected to standard atmospheric pressure to give true boiling temperatures.

A.3 Apparatus A.3.1 Distillation apparatus — As shown in Figure 1. A.3.2 Distillation flasks — 200 ml of borosilicate glass.

NOTE: 1. Liquid superheating in a new flask may be prevented by depositing a small amount of carbon in the bottom of the flask. This may be accomplished by heating and decomposing a pinch of tartaric acid in the bottom of the flask. The flask is then prepared for use by washing with water, rinsing with acetone, and drying.

A.3.3 Source of heat — An adjustable gas burner/electric heater so constructed that sufficient

heat can be obtained to distill the product at the uniform rate specified (see Note 1) for narrow range (less than 2 oC). An electric heater may be used only if it has been proven to give results comparable to those obtained using gas heat.

A.3.4 Receiver — A 100 ml cylinder graduated in 1 ml subdivisions and having an overall

height of 250 mm to 260 mm. A.3.5 Thermometers — Partial immersion type of the range –5 oC to 300oc with subdivisions

of 1 oC. Both bore corrections and either ice or steam standardization corrections are recommended.

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FIG. 1 — A.4 Safety precautions

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A.4.1 Most organic solvents and chemical intermediates will burn. In the operation of the

distillation apparatus, use a suitable catch pan and shielding to contain spilled liquid in the event of accidental breakage of the distillation flask.

A.5 Preparation of apparatus A.5.1 Clean and dry the condenser tub by swabbing with a piece of soft lint-free cloth

attached to a wire or cord or by any other suitable means. A.5.2 Center the thermometer into the neck of the flask through a tight fitting cork stopper so

that the upper end of the bulb is level with the lower side of the vapour tube at its junction with the neck of the flask.

NOTE: 2. It is far more important that the greatest volume of mercury be immersed in the refluxing

zone than that the immersion mark on the thermometer be placed at any specific point. A.5.3 Insert the vapour tube of the distillation flask into the condenser, making a tight

connection with a well-rolled cork. Adjust the position of the heater shield board so that the neck of the flask is vertical and the vapour tube extends into the condenser tube a distance of 25 mm to 50 mm. Have the bottom of the flask resting firmly in the 32 mm opening of the upper heat resistant board.

A.6 Procedure A.6.1 Using the graduated receiver, measure 100 ± 0.5 ml of the temperature adjusted

sample. Remove the flask from the apparatus and transfer the specimen directly to the flask, allowing the graduate to drain for 15 to 20 s.

A.6.2 Connect the flask to the condenser and insert the thermometer as described in Clause

A.5.2. Place the receiver, without drying, at the outlet of the condenser tube in such a position that the condenser tube extends into the graduate at least 25 mm but does not extend below the 100 ml mark. Place a flat cover on the top of the graduate to prevent the condensed moisture from entering the graduate.

A.6.3 Adjust the heat input so that the distillation proceeds at a rate of 4 to 5 ml/min

(approximately) 2 drops per second and move the receiving cylinder so that the tip of the condenser tube touches one side of the cylinder after the first drop falls (initial boiling point). Record the readings of the distillation thermometer after collecting 5 ml, 10 ml, 20 ml, 30 ml, 40 ml, 50 ml, 60 ml, 70 ml, 80 ml, 90 ml and 95 ml of distillate.

A.6.4 Without changing the heater setting, continue distillation beyond 95 per cent point unit

until the dry point is observed (Clause A.1.3). If dry point is not obtained (that is, if active decomposition should occur before the dry point is reached as evidenced by rapid evolution of vapour or heavy fumes; or if there is a liquid remaining on the bottom of the flask when the maximum temperature is observed on the distillation thermometer), record this fact.

A.6.5 When the dry point cannot be obtained, report as the end point, the maximum

temperature observed on the distillation thermometer. When active decomposition is encountered, the rapid evolution of vapour and heavy fumes is usually followed by a gradual decrease in the distillation temperature. If the expected drop in temperature does not occur, record the maximum temperature observed on the distillation thermometer after the 95 per cent point has been reached, and report as end point, 5 minimum. This notation shows that a true end point could not be reached within the given time limit. In any event, the end point should not exceed 5 minimum after the 95 per cent point.

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A.6.7 Record the barometric pressure A.6.8 Barometric correction — Correct each reading for deviation of the barometric

pressure from normal by adding algebraically the correction calculated as follows: Correction = k (760 - p) Where,

K = rate of change of boiling point with pressure in degrees Celsius per millimeter, and

P = Barometric pressure in millimeters of mercury at standard temperature. ANNEX B Determination of specific gravity at 20 oC B.1 Definition — Specific gravity is the ratio of the mass of a given volume of liquid at

20 oC to the mass of an equal volume of water at the same temperature. B.2 Apparatus B.2.1 Hydrometer glass graduated in units of relative density of total range 0.600 to 1.100

with a graduation interval of 0.001. B.2.2 Thermometers — Of total range of –5 to 250 oC with a graduation interval of 0.5. B.2.3 Hydrometer cylinder — Clear glass, or metal. For convenience in pouring, the cylinder

may have a lip on the rim. The inside diameter of the cylinder shall be at least 25 mm greater than the outside diameter of the hydrometer used in it. The height of the cylinder shall be such that the hydrometer floats in the sample with at least 25 mm clearance between the bottom of the hydrometer and the bottom of the cylinder.

B.2.4 Constant-temperature bath, for use when the sample requires a test temperature much

above or below room temperature. B.3 Procedure B.3.1 Adjust the temperature of the sample to 20 oC and bring the hydrometer cylinder and

thermometer to approximately the same temperature. B.3.2 Transfer the sample to a clean hydrometer cylinder without splashing to avoid formation

of bubble. Remove any air bubbles formed, after they have collected on the surface of the sample, by touching them with a piece of clean filter paper before inserting the hydrometer.

B.3.3 Place the cylinder containing the sample in a vertical position in a location free from air

currents. Ensure that the temperature of the sample does not change appreciably during the time necessary to complete the test; during this period, the temperature of the surrounding should not change by 2 oC. When testing at temperatures above room temperature a constant temperature bath may be necessary to avoid excessive temperature changes.

B.3.4 Lower the hydrometer gently into the sample. Take care to avoid wetting the stem

above the level to which it will be immersed in the liquid. Continuously stir the sample with the thermometer taking care that the mercury thread is kept fully immersed and that the stem of the hydrometer is not wetted above the immersion level. As soon as a steady reading is obtained, record the temperature of the sample to the nearest 0.25 oC and then remove the thermometer.

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B.3.5 Depress the hydrometer about two scale divisions into the liquid, and then release it.

The remainder of the stem of the hydrometer, which is above the level of the liquid, must be kept dry since unnecessary liquid on the stem affects the reading obtained. With samples of low viscosity, impart a slight spin to the hydrometer on releasing to assist in bringing it to rest, floating freely away from the walls of the cylinder. Allow sufficient time for the hydrometer to come to rest, and for all air bubbles to come to the surface. This is particularly necessary in case of more viscous samples.

B.3.6 When the hydrometer has come to rest, floating freely away from the walls of the

cylinder, estimate the hydrometer scale reading to the nearest 0.000 1 relative density. The correct hydrometer reading is that point on the hydrometer scale at which the principal surface of the liquid cuts the scale. Determine this point by placing the eye slightly below the level of the liquid and slowly raising it until the surface first seen as distorted eclipse, appears to become a straight line cutting the hydrometer scale.

ANNEX C Determination of the refractive index Leave the sample in a conditioned room overnight and read out its refractive index the

following morning using a suitable Refractometer; of range 1.300 to 1.700. ANNEX D Determination of aromatic content D.1 Principle — A small quantity of the sample is introduced into a special glass

adsorption column packed with fine activated silica gel, a small layer of which contains a mixture of fluorescent dyes. When all the sample has been adsorbed on the gel, alcohol is added to desorb the sample and force it down the column. The hydrocarbons are separated according to their adsorption affinities into aromatics, olefins and saturated hydrocarbons. The fluorescent dyes are also separated selectively, with the hydrocarbon types, to make the boundaries of the aromatics, olefin and saturate zones visible under ultraviolet light. The percentage volume of each hydrocarbon type is calculated from the length of each zone in the column. Some diolefins and aromatics with olefins side chains, plus any sulphur, nitrogen, and oxygen compounds are determined as aromatics.

D.2 Reagents and materials D.2.1 Silica gel, of 150µm to 75µm particle size, manufactured to ensure minimum olefin

polymerization activity and to conform to the sieve test requirements shown in Table 2. It is necessary to screen the gel to make certain that the size specification is met. Before use, dry the gel in a shallow vessel at 175 ± 2 oC for 3 hours. Transfer the dried gel to an airtight container while still hot, and protect it thereafter from atmospheric moisture.

TABLE 2. SIEVE ACCEPTANCE TESTS OF SILICA GEL

MESH APERTURE OF SIEVE

µ m

PERCENTAGE PASSING (m/m)

180

150

75

100

95 min.

15 max

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D.2.2 Fluorescent indicator dyed gel, consisting of a mixture or recrystallized Petrol Red AB4

and purified portions of the olefin and aromatic dyes obtained by chromatographic adsorption following a definite, uniform procedure, and deposited on silica gel.

It is essential that the dyed gel be stored in a dark place under an atmosphere of

nitrogen. Even under these conditions the fluorescent dyes can deteriorate resulting in indistinct zone boundaries. Batches stored for longer than six months should be considered suspect.

D.2.3 Isopropyl alcohol (propan-2-01), refined, 99 per cent grade. D.2.4 Pressuring gas, air (or nitrogen) delivered to the top of the column at pressures

controllable over the range 0 to 103.4 kN/m2 (0 to 1.05 kgf/cm2 gauge). D.3 Apparatus D.3.1 Adsorption columns, made of glass with standard wall tubing as shown in Figure 2(a),

or with precision bore tubing as shown in Figure 2(b), and consisting of a charger section with a capillary neck, a separator section, and an analyzer section.

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FIG. 2 — ALTERNATIVE ADSORPTION COLUMNS WITH STANDARD WALL AND PRECISION BORE TUBING IN ANALYSER

D.3.1.1 For normal laboratory procedure use standard wall tubing for the analyzer section. It

is necessary to select tubing of uniform bore and to provide a leakproof connection between the separator and the analyzer sections. Draw out one end of the tubing selected for the analyzer section to a fine capillary to retain the gel. Connect the other end of the analyzer section to the separator section with a 30 mm length of PVC tubing, making certain that the two glass sections touch. To ensure a leakproof

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glass-to-PVC, then insert the upper end of the analyzer section into the PVC sleeve. Alternatively, this seal can be made by securing the PVC sleeve to the analyzer section by wrapping it tightly with soft wire.

NOTE: Calibrations of standard wall tubing would be impractical; however, any variations of 0.5 mm or

greater, as measured by ordinary calipers, in the outside diameter along the tube may be taken as an indication of irregularities in the inner diameter and such tubing shall not be used.

D.3.1.2 For reference purposes use precision bore tubing. The inner diameter of the analyzer

section shall be 1.60 mm to 1.65 mm and an approximately 100 mm thread of mercury shall not vary in length by more than 0.3 mm when located in any part of the analyzer section. In glass-sealing the various sections to each other, long-taper connections shall be made instead of shouldered connections. Support the silica gel by means of a 6 mm diameter portion of phosphor-bronze or equivalent 75 µ m

aperture wire gauge located between the ball and socket of the S 13 spherical joint and covering the analyzer outlet. The column tip attached to the S 13 socket shall have a 2 mm internal diameter.

Clamp the ball and socket together and ensure that the tip does not tend to slide from

a position in a direct line with the analyzer section during the packing and subsequent use of the column.

D.3.2 Zone-measuring device — The zones may be marked with a glass-writing pencil and

the distances measured with a metre rule, with the analyzer section lying horizontally. Alternatively, the metre rule may be fastened adjacent to the column. In this case, it is convenient to have each rule fitted with four movable metal index clips (see Figure 2) for marking zone boundaries and measuring the length of each zone.

D.3.3 Ultraviolet light source, with radiation predominantly at 365 nm. A convenient

arrangement consists of one or two units about 900 mm to 1 200 mm long mounted vertically along the apparatus, and adjusted to give the best fluorescence.

D.3.4 Vibrator, for packing the silica gel by vibrating individual columns or the frame

supporting multiple columns. A small electric vibrator is recommended, but any other means may be used to obtain a uniform packing.

D.3.5 Hypodermic syringe, capacity 1 ml, graduated in 0.01 ml or 0.02 ml, with a needle 100

ml in length. Needless of external diameter 0.7 mm to 1.2 mm are convenient to use. D.4 Preparation of apparatus —Mount the apparatus assembly in a darkened room or

area to facilitate observation of zone boundaries. For multiple determinations, assemble an apparatus which includes the ultraviolet light source, a rack to hold the columns, and a gas manifold system with spherical joints to connect to the desired number of columns.

NOTE: Any other related suitable apparatus can be used. D.5 Procedure D.5.1 Prepare two standard wall columns for simultaneous, duplicate analysis of each

sample, or a single column if precision bore tubing is to be used. Freely suspend each column from a loose-fitting clamp placed immediately below the spherical joint of the charger section. While vibrating the column along its entire length, add small increments of silica gel through a glass funnel into the charger section until the separator section is half full. Stop the vibrator and add a 3 mm to 5 mm layer of dyed gel. Start the vibrator and vibrate the column while adding additional silica gel. Continue to add silica gel until the tightly packed gel extends 75 mm into the charger section. Wipe the length of the column with a damp cloth while vibrating the column. This aids in packing the column by removing static electricity. Vibrate the column with a damp cloth while vibrating the column. This aids in packing the column by

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removing static electricity. Vibrate the column after filling is completed. Vibration for about 4 min is usually satisfactory when the vibrator is used.

NOTE: More than one pair of columns can be prepared simultaneously by mounting them on a frame or

rack to which an electric vibrator is attached. D.5.2 Attach the filled columns to the apparatus assembly in the darkened room or area, and

when a permanently mounted metre rule is used, fasten the lower end of the column to the zone measuring device fixed with a rubber band.

D.5.3 Chill the sample and the hypodermic syringe to between 2 oC and 4 oC. Draw 0.75 ±

0.03 ml of sample into the syringe and inject the sample 30 mm below the surface of the gel in the charger section.

D.5.4 Fill the charger section to the spherical joint with isopropyl alcohol. Connect the column

to the gas manifold and apply 13.8 kN/m2 (0.14 kgf/cm2) gas pressure for 2.5 min, to move the liquid front down the column. Increase the pressure to 34.5 kN/m2 (0.35 kgf/cm2) for another 2.5 min and then adjust the pressure required to give a transit time of about 1 hour. Usually 68.9 to 103.4 kN/m2 (0.7 to 1.05 kgf/m2) gas pressure is needed. The pressure required will depend on the tightness of packing of the gel and the molecular mass of the sample. A transit time of 1 hour is generally satisfactory; however, high-molecular mass samples may require longer transit times.

D.5.5 Before commencing to read the zone boundaries, carefully wipe the outside of the

column with a cloth dampened with ethanol and avoid handling the column with bare hands thereafter.

D.5.6 After the red, alcohol-aromatic boundary has advanced 350 mm into the analyzer

section, make a set of readings by quickly marking the boundary of each of hydrocarbon-type zone observed in ultraviolet light (see Note 1) in the following sequence: (CAUTION — Avoid touching the column with the hand during this operation).

— for the non-fluorescent saturate zone, mark the front of the charge and the

point where the yellow fluorescence first reaches its maximum intensity;

— for the upper end of the second, or olefin zone, mark the point where the first intense blue fluorescence occurs;

— finally , for the upper end of the third or aromatic zone, mark the upper end of

a reddish or brown zone (see Note 2). With colourless distillates, the alcohol-aromatic boundary is clearly defined by a red ring of dye. However, certain impurities may obscure this red ring and give a brown colouration which varies in length, but which shall be counted as a part of the aromatic zone, except that when no blue fluorescence is present, the brown or reddish ring shall be considered as part of the next distinguishable zone below it in the column. If the boundaries have been marked off with index clips, record the measurements. NOTES: 1. CAUTION — Direct exposure to ultraviolet light can be harmful, and operators should

avoid this as far as possible, particularly with regard to their eyes.

2. When zone boundaries are indistinct, the use of a Wratten No. 47 or No. 50 light filter between the column and the eyes may aid in recognizing the aromatic zone front.

D.5.7 When the sample has advanced another 50 mm down the column, make a second set

of readings by marking the zones in the reverse order as described in Clause 5.5.5.6 so as to minimize errors due to the advancement of boundary positions during readings. If the marking to mark off each set of measurements, and the distances measured at the end of the test with the analyser sections lying horizontally on the

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bench top. If the boundaries have been marked off with index clips, records the measurement.

NOTE: Erroneous results can be caused by improper packing of the gelor incomplete elution of hydrocarbons by the alcohol. With precision bore columns, incomplete elution can be detected from the total length of the several zones, which must be at least 500 mm for a satisfactory analysis. With standard will tubing, this criterion of total sample length is not strictly applicable because the inside diameter of the analyzer is not the same in all columns. For samples containing substantial amounts of material boiling above 204o C, the use of isoamyl alcohol instead of isopropyl alcohol may improve elution. D.5.8 Release the gas pressure and disconnect the column. Discard the analyzer section

after all measurements have been completed if the standard wall column is used. To remove used gel from the precision bore column, invert it above a sink and insert through the wide end a long piece of about 1 mm diameter hypodermic tubing with a 45o angle tip. By means of 6mm tubing at the opposite end for attaching a rubber tube, connect to a water tap and flush with a rapid stream of water. Rinse with residue –free acetone (reagent grade preferred) and dry by evacuation.

D.6 Calculation D.6.1 For each set of observations (four for the two standard wall columns and two for the

precision bore column), calculate to the nearest 0.1 per cent the volume per cent of the hydrocarbon types as follows:

Aromatics, per cent )/( vv = L

La X 100

Olefins, per cent )/( vv = L

Lo X 100

Saturates, per cent )/( vv = L

Ls X 100

Where,

aL = the length, in millimeters, of the aromatic zone;

oL = the length, in millimeters, of the olefin zone;

sL = the length, in millimeters, of the saturate zone; and

L = the sum of aL + oL + sL .

D.6.2 If the standard wall column is used, calculate average of the four sets of observations obtained from two successive sets of readings on each pair of columns. D.6.3 If the precision bore column is used, calculate the average from two successive

readings obtained on a single column. D.6.4 Round off to the nearest 0.1 per cent the values obtained by using the precision bore,

column, and to the nearest 1 per cent those obtained by using the standard wall column, in both cases adjusting if necessary the amount of the largest component in order that the sum of the components is 100 per cent.

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D.7 Expression of Results — Report, as volume per cent of aromatic content in the sample as analysed, the rounded value obtained as detailed in clause 5.5.6.4 and state whether the standard wall column or the precision bore column was used

Annex E Determination of residue on evaporation E.1 Note: — Residue on evaporation: The amount of nonvolatile residue obtained under the conditions of test. E.2 Apparatus E.2.1 Evaporation bath, either a solid metal-block bath using a metal of high thermal

conductivity, or a liquid bath fitted with a reflux condenser, electrically heated and constructed in accordance with the general principles shown in Figure 3. The electric supply to the liquid bath shall be sufficient to keep the Liquid boiling through the preheating coil at the specified rate. The evaporation bath shall be provided with wells and air jets for three or more beakers and be insulated. The preheaters, manifolds, and air outlets shall be so constructed as to allow the required rate of air flow (see Clause E.2.2). The beaker wells shall be made sufficiently deep to allow insertion of the 100 ml beakers to a depth of 70 mm. If a liquid bath is used, it shall be filled to within 25 mm of the top with a stable liquid having a boiling point within 160o C and 165o C; (ethylene glycol) containing approximately 3 per cent of

water is suitable for this purpose. E.2.2 Air supply apparatus, capable of supplying filtered air at a pressure not greater than

34.5 kN/m2 (0.35 kgf/cm2) to the inlet of the preheating coil of the bath, and at a rate sufficient to provide a flow from each outlet of 1 000 ± 150 ml/s at a temperature of 155 ± 5o C.

E.2.3 Flowmeter, capable of metering a flow of air equivalent to 1 000 ml/s for each outlet of the evaporation bath at the operating temperature. The use of a calibrated flowmeter allowing a flow of 600 ± 90 ml/s, measured at room temperature, will ensure delivery of 1 sml /90000 ± at the operating temperature, provided that the pressure at the outlet of the flowmeter is not greater than 34.5 kN/m2 (0.35 kgf/cm2). E.2.4 Beakers, of 100 ml capacity, flat bottomed as shown in Figure 3. The beakers shall

be arranged in sets, the number in each set depending on the number of beaker wells in the evaporation bath

E.2.5 Cooling vessel; suitable covered vessel for cooling the beakers before weighing, such as a glass desiccator or a tightly covered metal vessel for each set of beakers. A drying agent is not to be used in the cooling vessel.

E.2.6 Balance, having a sensitivity of at least 0.1 mg, preferably with no drying

agent in the case. E.2.7 Thermometer, of the mercury-in-glass type, nitrogen-filled, graduated on the stem, enamel-baked, adjusted for 76 mm immersion and allowing temperature in the range 150o C to 160o C to be measured with an accuracy

of ± 1o C at an average temperature of the mergent mercury column of 65o C (see note on Clause A.5.2).

E.3 Cleaning Liquids E.3.1 A mixture of equal volumes of toluene and acetone, of analytical reagent quality. E.3.2 Chromic/sulphuric acid solution E.4 Preparation of Apparatus

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E.4.1 Assemble the apparatus as shown in Figure 3. With the apparatus at

roomtemperature, adjust the air flow to a rate of 600 ml/s at one of the outlets. Measure the flow at the remaining outlets and make any necessary adjustments so that the rate at each outlet is 600 ± 90 ml/s (see E.2.3). Heat the bath and when its temperature reaches 160o C to 165o C, place a beaker in each well (E.2.1). Submit air at the rate required

with the conical jets in position. Check the temperature in each well by placing the bulb of the thermometer on the bottom of the beaker in the well. Do not use any well where the temperature does not lie between 150o C and 160o C.

E.4.2 Clean new beakers by immersion in the chromic/sulphuric acid solution (E.3.2) for at

least 6 hours. Remove the beakers from the solution by means of stainless steel forceps and handle only with forceps thereafter. Wash the beakers thoroughly, first with tap water, then with distilled water. NOTE Protective clothing such as gloves and goggles must be worn by operators using

chromic/sulphuric acid solution. Clean beakers which have been used in previous determinations by removing the residue with the mixture (E.3.1), then immerse them for at least 6 h in

chromic/sulphuric acid cleaning solution followed by washing as described above. Clean the tare beakers in a similar manner. Dry the beaker for 1 hour in an oven at 150o C and allow them to cool for at least 2 h in the cooling vessel placed in the vicinity of the balance.

E.5 Procedure — For each sample, weigh to the nearest 0.1 mg two test beakers for a

duplicate determination, using analytical balance. Repeat the weighings without changing the order in which the beakers are weighed, until consecutive masses for the beakers agree within 0.1 mg, and record the masses. If suspended or solid matter is present, mix the contents of the sample container thoroughly. Immediately filter, at atmospheric pressure, the necessary quantity of the sample through a sintered-glass funnel of porosity grade p.100 (pore size index 40 mµ to 100 mµ ).

Using a graduated measuring cylinder, pour 50 ml of the sample into each test beaker. Place the full beakers and also the empty tare beaker in the evaporation bath, previously heated to the specified temperature (160o C to 165o C). Replace the conical jet as each beaker is filled, centering the jet vertically above the surface of the liquid. The time elapsing between filling the first and second beakers shall be as short as possible. Supply air at the required rate. After 30 min evaporation, remove the beakers from the bath, place them in the cooling vessel and allow to cool in the vicinity of the balance for at least 2 h. Weigh the beakers in the same manner and in the same sequences as was followed previously, repeating the weighings until consecutive masses agree within 0.1 mg. If the results of the two evaporations differ by more than 1.0 mg, repeat the determinations.

E.6 Expression of Results E.6.1 Calculate the residue on evaporation A, in milligrams per 100 ml, by the formula.

A = 2 000 (m1 - mo)

Where, M1 = the mass, in grams, of the test beaker plus residue; and

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Mo = the mass, in grams, of the empty test beaker E.6.2 Report the mean of the sum of the results of the duplicate determinations to the

nearest milligram per 100 ml as the residue on evaporation. After the numerical value designated by the word ‘filtered ‘ if the sample has been so treated.

E.7 Precision — For results of the order of 10 mg/100 ml (i.e. the maximum permitted residue), duplicate results shall not be considered suspect unless they differ by more

than 3 mg/100 ml (repeatability) or 6 mg/100 ml (reproducibility). Annex F Determination of sulphur content F.1 Summary of Method F.1.1 A liquid sample is injected into a combustion tube maintained at about 800o C having a flowing stream of gas containing about 80 per cent oxygen and 20 per cent

inert gas (for example, nitrogen, argon, etc.). Oxidative pyrolysis converts the sulphur to sulphur dioxide which then flows into a titration cell where it reacts with triiodide ion present in the electrolyte. The triiodide thus consumed, is coulometrically replaced and the total current required to replace it is a measure of the sulphur present in the sample injected.

F.1.2 The reaction occurring in the titration cell as sulphur dioxide enters is

I3 - +SO2 +H2O →SO3 +3I - + 2H+

The triiodide ion consumed in the above reaction is generated coulometrically thus: 3I - → I3

- + 2e- F.1.3 These microequivalents of triiodide (iodine) are equal to the number of

microequivalents of titratable sample ion entering the titration cell.

F.2 Significance F.2.1 This method is used to determine trace quantities of sulphur in reformer charge

stocks and similar petroleum fractions where such trace concentrations of sulphur are deleterious to the performance and life of the catalyst used in the process. Higher concentrations of sulphur in products analyzed by this method after appropriate dilution are often detrimental to the use of the product.

F.3 Apparatus F.3.1 Pyrolysis furnace — The sample should be pyrolized in electric furnace having having

at least two separate and independently controlled temperature zones, the first being an inlet section that can maintain a temperature sufficient to volatilize all the organic sample. The second zone shall be a pyrolysis section that can maintain a temperature sufficient to pyrolyze the organic matrix and oxidize all the organically bound sulphur. A third outlet temperature zone is optional.

F.3.1.1 Pyrolysis furnace temperature zones for light liquid petroleum hydrocarbons should be variable as follows; Inlet zone up to at least 700o C Center pyrolysis zone 800o C to 1 000o C Outlet zone (optional) up to at least 800o C F.3.2 Pyrolysis tube, fabricated from quartz and constructed in such a way that a sample, which is vapourized completely in the inlet section is swept into the pyrolysis zone by

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an inert gas where it mixes with oxygen and is burned. The inlet end of the tube shall hold a septum for syringe entry of the sample and side arms for the introduction of oxygen and inert gases. The center or pyrolysis section should be of sufficient

volume to ensure complete pyrolysis of the sample. F.3.3 Titration cell, containing a sensor-reference pair of electrodes to detect changes in triiodide ion concentration and a generator anode-cathode pair of electrodes to

maintain constant triiodide ion concentration and an inlet for a gaseous sample from the pyrolysis tube. The sensor electrode shall be platinum foil and reference electrode platinum wire in saturated triiodide half-cell. The generator anode and cathode half-cell shall also be platinum. The titration cell shall be placed on a suitable magnetic stirrer. NOTE Caution – Excessive speed will decouple the stirring bar, causing it to rise in the cell and damage The electrodes. The creation of a slight vortex is adequate.

F.3.4 Microcoulometer, having variable attenuation, gain control, and capable of measuring the potential of the sensing-reference electrode pair, and comparing this potential

with bias potential, amplifying the potential difference, and applying the amplified difference to the working-auxiliary electrode pair so as to generate titrant. Also the microcoulometer outlet voltage signal shall be proportional to the generating current.

F.3.5 Recorder, having a sensitivity of at least 0.1 mV/in. with chart speeds of ½ to 1 in./min. Use of a suitable electronic or mechanical integrator is recommended but

optional. F.3.6 Sampling syringe — A microlitre syringe of lµ capacity capable of accurately

delivering 1 lµ of sample into the pyrolysis tube. 3-in by 24-gauge needles are recommended to reach the inlet zone of the pyrolysis furnace. NOTE Since care must be taken not to overload the pyrolyzing capacity of the tube by too fast a sample

Injection rate, means should be provided for controlling the sample addition rate (0.1 lµ /s to 0.2

lµ /s).

F.4 Reagents and materials F.4.1 Purity of reagents — Analytical grade chemicals shall be used in all tests. F.4.2 Purity of water — The water used in preparing the cell electrolyte should be

demineralized or distilled or both. Water of high purity is essential. NOTE Distilled water obtained from all borosilicate glass still, fed from a demineralizer, has proven Very satisfactory.

F.4.3 Acetic acid (sp.gr.1.05) — Glacial acetic acid (CH3COOH). Caution: See Clause J.1

F.4.4 Argon, helium, or nitrogen, high purity grade (HP), used as carrier gas. (Caution – Compressed gas under high pressure. Gas reduces oxygen available for breathing. See Clause J.2) NOTE High-purity grade gas has a minimum purity of 99.995 per cent. F.4.5 Cell electrolyte solution— Dissolve 0.5g of potassium iodide (KI) and 0.6 g of sodium

Azide (NaN3) in approximately 500 ml of high-purity water, add 5 ml of acetic acid (CH3COOH) and dilute to 1 000 ml. NOTE Bulk quantities of the electrolyte should be stored in a dark bottle or in a dark place and be

prepared fresh at least every 3 months. F.4.6 Gas regulators — Two-stage gas regulators must be used on the reactant and

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Carrier gas. F.4.7 Iodine (I) — 20 mesh or less, for saturated reference electrode. F.4.8 Isooctane (2,2,4-trimethylpentane) — Caution: See Clause .3. Form of cyclohexane (boiling point 176 oF (80 oC)isooctane (2,2,4-trimethylpentane) (boiling point, 211 oF (99.3 oC)).or hexadecane (boiling point, 549.5 0F (287.5 oC)) F.4.9 n-Butyl sulphide (CH3CH2CH2CH2)2S

F.4.10 Oxygen, high purity grade (HP)4, used as the reactant gas. (Warning – Oxygen vigorously accelerates combustion. See clause J.4.)

F.4.11 Potassium iodide (KI), fine granular. F.4.12 Sodium azide (NaN3), fine granular F.4.13 Sulphur, standard solution (approximately 30 ppm) — Pipette 10 ml of sulphur

stock solution (reagent 6.14) into a 100-ml volumetric flask and dilute to volume with isooctane. NOTE The analyst may choose other sulphur compounds for standards appropriate to sample boiling

range and sulphur type which cover the concentration range of sulphur expected. F.4.14 Sulphur, standard stock solution (approximately 300 ppm) — Weigh accurately

0.500 0 g of n-butyl sulphide into a tared 500-ml volumetric flask. Dilute to the mark with isooctane and reweigh.

S, ppm = g of n-butyl sulphide × 0.2187 × 106 g of (n-butyl sulphide + solvent)

F.5 Preparation of Apparatus F.5.1 Carefully insert the quartz pyrolysis tube in the pyrolysis furnace and connect the

Reactant and carrier gas lines. F.5.2 Add the electrolyte solution to the titration cell and flush several times. Maintain an Electrolyte level of 1/8 to 1/4 in. (3.2 mm to 6.4 mm) above the platinum electrodes. F.5.3 Place the heating tape on the inlet of the titration cell. F.5.4 Place the titration cell on the magnetic stirring deceive and connect the cell inlet to

the outlet end of the pyrolysis tube. Position the platinum foil electrodes (mounted on the movable cell head) so that the gas inlet flow is parallel to the electrodes with the generator anode adjacent to the generator cathode. Assemble and connect the coulometer and recorder (integrator optional) as designed or in accordance with the manufacturer’s instructions. Figure 3.2 illustrates the typical assembly and gas flow through a coulometric apparatus.

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FIG. 3– FLOW DIAGRAM FOR COULOMETRIC APPARATUS FOR TRACE

SULPHUR DETERMINATION

F.5.4.1Turn the tape heater on F.5.5 Adjust the flow of the gases, the pyrolysis furnace temperature, titration cell, and the

coulometer to the desired operating conditions. Typical operational conditions are given in table 3.

F.6 Calibration and Standardization F.6.1 Prepare a series of calibration standards covering the range of sulphur concentration

expected. Follow instructions in Clauses F.4.13, F.4.14, or dilute to appropriate level with isooctane.

F.6.2 Adjust the operational parameters (Clause 7.5.6.5) F.6.3 The sample size can be determined either volumetrically or by mass. The sample

size should be 80 percent or less of the syringe capacity. F.6.3.1 Volumetric measurement can be obtained by filling the syringe with about 8 lµ or

less of sample, being careful to eliminate bubbles, retracting the plunger so that the lower liquid meniscus falls on the 1- lµ mark, and recording the volume of liquid in the syringe. After the sample has been injected, again retract the plunger so that the lower liquid meniscus falls on the 1- lµ mark, and record the volume of liquid in

the syringe. The difference between the two volume readings is the volume of sample injected.

F.6.3.2 Alternatively, the sample injected device may be weighed before and after the injection to determine the amount of sample injected. This method provides greater precision than the volume delivery method, provided that a balance with a

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precision of ± 0.000 01 g is used. F.6.4 Insert the syringe needles through the inlet septum up to the syringe barrel and inject the sample or standard at an even rate not to exceed 0.1 lµ /s to 0.2 lµ /s. If a microlitre syringe is used with an automatic injection rate (volume/pulse) should be calibrated to deliver 0.1 lµ /s to 0.2 lµ /s. F.6.5 Repeat the measurement of each calibration standard at least three times. NOTE Not all of the sulphur in the sample comes through the furnace as titratable SO2. In the strongly oxidative conditions of the pyrolysis tube some of the sulphur is also converted to SO3 which does not react with the titrant. Accordingly, sulphur standards of n-butyl sulphide in isooctane or sulphur standards appropriate to sample boiling range and sulphur type and

sulphur concentration should be prepared to guarantee adequate standardization. Recoveries less than 75 per cent are to be considered suspect. Low recoveries are an indication to the operator that he should check his parameters, his operator that he should check his parameters, his operating techniques, and his coulometric system. If the instrument is being operated properly recoveries between 75 and 90 per cent are to be expected. Satisfactory standard materials are given in Table 4.

F.6.6 If the fraction of sulphur converted to SO2 drops below 75 per cent of the standard solutions, fresh standard solutions should be prepared. If a low conversion factor persists, procedural details should be reviewed. F.7 Procedure F.7.1 Flush the 10- lµ syringe several times with the unknown sample. Determine the Sulphur concentration in accordance with Clauses F.1 to F.5. F.7.2 Sulphur concentration may require adjustment of sensitivity settings or sample volume or both. F.8 Calculations F.8.1 Calculate the sulphur content of the sample in parts per million, ppm, by mass as Follows: Sulphur, ppm gg /µ = (A ×1.99) / (R×M×F)

Sulphur, ppm = (A ×1.99 × 10 3 ) / (R×V×D×F) Where,

A = area under curve, R = coulometer range switch setting, M = mass of sample, g (volume X density), V = volume of sample, lµ D = density of sample, g/ml, and F = recovery factor, fraction of sulphur in standard that is titrated, ratio of ppm sulphur determined in standard divided by the known ppm sulphur in standard.

F = (A X 1.99) / (RXMCstd) Where, C

std= concentration of standard, ppm. F.9 Precision F.9.1 The precision of the method as obtained by statistical examination of interlaboratory test results is as follows:

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F.9.1.1 Repeatability — The difference between successive test results by the same apparatus under constant operating conditions on identical test material would, in the long run, in the normal and correct operation of the test method exceed 28 per cent of the average value only in one case in twenty. F.9.1.2 Reproducibility — The difference between two single and independent results obtained by different operators working in different laboratories on identical test material would, in the long run, in the normal and correct operation of the test method exceed 38 per cent of the average only in one case in twenty.

TABLE 3. TYPICAL OPERATIONAL CONDITIONS Reactant gas flow (oxygen), cm3/min

160

Carrier gas flow (Ar, He, N), cm3/min

40

Furnace temperature; oC: Inlet zone Pyrolysis zone Outlet zone

700 800 800

Titration cell

Stirrer speed set to produce slight vortex

Coulometer: Bias voltage, mV Gain

160 Low (approximately 200)

TABLE 4. SATISFACTORY STANDARD MATERIALS

Sample Type

Boiling point Range oF (oC)

Sulphur compound

Naphthas

80 to 400 (26 to 204)

Cyclohexane Sulphide

Jet fuels and stove oil 350 to 525 (177 to 274)

Benzyl-thiophene

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Center furnace temperature Oxidative sulphur system: Thiophene in Cyclohexane (10 ppm 5) using 0.06 per cent oxide electrolyte.

Flow rate (cc/min)

Legend Oxygen Argon O2/Ar ratio

40

160

1:4

100

100

1:1

160

40

4:1

FIG. 4 – PER CENT RECOVERY VERSUS TEMPERATURE ( OC)

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Annex G Determination Of Freedom From Objectable Su lphur Compounds

A copper strip is inserted in the distillation flask during the determination of the initial boiling point and dry point (Annex B) and the tarnishing of the strip examined at the end of this experiment. Annex H Determination Of Flash Point H.1 Summary of Test Method H.1.1 A brass test cup of specified dimensions, filled to the inside mark with test specimen and fitted with a cover of specified dimensions, is heated and the specimen stirred at specified rates. An ignition source is directed into the test cup at regular intervals with simultaneous interruption of the stirring, until a flash is detected. The flash point shall be 40oC minimum I.2 Significance and Use H.2.1 The flash point temperature is one measure of the tendency of the test specimen to form a flammable mixture with air under controlled laboratory conditions. It is only one of a number of properties which must be considered in assessing the overall flammability hazard of a material. H.2.2 These test methods should be used to measure and describe the properties of materials, products, or assemblies in response to heat and an ignition source under controlled laboratory conditions and should not be used to describe or appraise the fire hazard or fire risk of materials, products, or assemblies under actual fire conditions. However, results of these test methods may be used as elements of a fire risk assessment which takes into account all of the factors which are pertinent to an assessment of the fire hazard of a particular end use. H.2.3 These test methods provide the only closed cup flash point test procedures for temperatures up to 370°C (698°F). H.3 Apparatus H.3.1 Pensky-Martens Closed Cup Apparatus (manual)—This apparatus consists of the test cup, test cover and shutter, stirring device, heating source, ignition source device, air bath, and top plate described in detail in H.10. The assembled manual apparatus, test cup, test cup cover, and test cup assembly are illustrated in Figs. A1.1-A1.4, respectively. Dimensions are listed respectively. H.3.2 Pensky-Martens Closed Cup Apparatus (automated)— This apparatus is an automated flash point instrument that is capable of performing the test in accordance with H.7 (Procedure A) and H.8 (Procedure B) of these test methods. The apparatus shall use the test cup, test cover and shutter, stirring device, heating source, and ignition source device described in detail in H.10. H.3.3 Temperature Measuring Device—Thermometer or an electronic temperature measuring device, such as resistance thermometers or thermocouples. The device shall exhibit the same temperature response as the mercury thermometers. H.3.4 Ignition Source—Natural gas flame, bottled gas flame, and electric igniters (hot wire) have been found acceptable for use as the ignition source. The gas flame device described in

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detailed in Fig. A1.4 requires the use of the pilot flame described in H.10. The electric igniters shall be of the hot-wire type and shall position the heated section of the igniter in the aperture of the test cover in the same manner as the gas flame device. (Warning— Gas pressure supplied to the apparatus should not be allowed to exceed 3 kPa (12 in.) of water pressure.) H.3.5 Barometer—With accuracy of 60.5 kPa. NOTE:—The barometric pressure used in this calculation is the ambient pressure for the laboratory at the time of the test. Many aneroid barometers, such as those used at weather stations and airports, are precorrected to give sea level readings and would not give the correct reading for this test. H.4. Reagents and Materials H.4.1 Cleaning Solvents—Use suitable solvent capable of cleaning out the specimen from the test cup and drying the test cup and cover. Some commonly used solvents are toluene and acetone. (Warning —Toluene, acetone, and many solvents are flammable and a health hazard. Dispose of solvents and waste material in accordance with local regulations.) H.5 Sampling Successive test specimens can be taken from the same sample container. Erroneously high flash points may be obtained if precautions are not taken to avoid the loss of volatile material. Do not open containers unnecessarily, to prevent loss of volatile material or possible introduction of moisture, or both. Samples for storage shall be capped tightly with inner seals. Do not make a transfer unless the sample temperature is at least the equivalent of 18°C or 32°F below the expected flash point. Do not store samples in gas-permeable containers, since volatile material may diffuse through the walls of the enclosure. Samples in leaky containers are suspect and not a source of valid results. NOTE —Volatile vapors can escape during heating when the sample container is not properly sealed. H.6. Preparation of Apparatus H.6.1 Support the manual or automated apparatus on a level steady surface, such as a table. H.6.2 Tests are to be performed in a draft-free room or compartment. Tests made in a laboratory hood or in any location where drafts occur are not reliable. NOTE —A shield, of the approximate dimensions 460 mm (18 in.) square and 610 mm (24 in.) high, or other suitable dimensions, and having an open front is recommended to prevent drafts from disturbing the vapors above the test cup. NOTE —With some samples whose vapors or products of pyrolysis are objectionable, it is permissible to place the apparatus along with a draft shield in a ventilation hood, the draft of which is adjustable so that vapors can be withdrawn without causing air currents over the test cup during the ignition source application period. H.6.3 Prepare the manual apparatus or the automated apparatus for operation in accordance with the manufacturer’s instructions for calibrating, checking, and operating the equipment. (Warning— Gas pressure should not be allowed to exceed 3 kPa (12 in.) of water pressure.) H.6.4 Thoroughly clean and dry all parts of the test cup and its accessories before starting the test, to ensure the removal of any solvent which had been used to clean the apparatus. Use suitable solvent capable of removing all of the specimen from the test cup and drying the test cup and cover. Some commonly used solvents are toluene and acetone. (Warning— Toluene, acetone, and many solvents are flammable health hazard) PROCEDURE A H.7 Procedure H.7.1Manual Apparatus:

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Fill the test cup with the test specimen to the filling mark inside of the test cup. The temperature of the test cup and test specimen shall be at least 18°C or 32°F below the expected flash point. If too much test specimen has been added to the test cup, remove the excess using a syringe or similar device for withdrawal of fluid. Place the test cover on the test cup and place the assembly into the apparatus. Be sure the locating or locking device is properly engaged. If the temperature measuring device is not already in place, insert the device into its holder. Light the test flame, and adjust it to a diameter of 3.2 to 4.8 mm (0.126 to 0.189 in.), or switch on the electric igniter and adjust the intensity in accordance with the manufacturer’s instructions. (Warning— Gas pressure should not be allowed to exceed 3 kPa (12 in.) of water pressure.) (Warning— Exercise care when using a gas test flame. If it should be extinguished it will not ignite the vapors in the test cup, and the gas for the test flame that then enters the vapor space can influence the result.) (Warning— The operator should exercise and take appropriate safety precautions during the initial application of the ignition source, since test specimens containing low-flash material can give an abnormally strong flash when the ignition source is first applied.) (Warning— The operator should exercise and take appropriate safety precautions during the performance of these test methods. The temperatures attained during these test methods, up to 370°C (698°F), are considered hazardous.) Apply the heat at such a rate that the temperature, as indicated by the temperature measuring device, increases 5 to 6°C (9 to 11°F)/min. Turn the stirring device at 90 to 120 rpm, stirring in a downward direction. (Warning— Meticulous attention to all details relating to the ignition source, size of test flame or intensity of the electric igniter, rate of temperature increase, and rate of dipping the ignition source into the vapor of the test specimen is desirable for good results.) H.7.1.1 Application of Ignition Source:

a) If the test specimen is expected to have a flash point of 110°C or 230°F or below, apply the ignition source when the temperature of the test specimen is 23 + 5°C or 41 + 9°F below the expected flash point and each time th ereafter at a temperature reading that is a multiple of 1°C or 2°F. Disconti nue the stirring of the test specimen and apply the ignition source by operating the mechanism on the test cover which controls the shutter so that the ignition source is lowered into the vapor space of the test cup in 0.5 s, left in its lowered position for 1 s, and quickly raised to its upward position.

b) If the test specimen is expected to have a flash point above 110°C or 230°F, apply

the ignition source in the manner described above at each temperature increase of 2°C or 5°F, beginning at a temperature of 23 + 5°C or 41 + 9°F below the expected flash point. (Warning— As a safety practice, when using automated apparatus, it is strongly advised that, for an expected flash point above 130°C, to dip the igniter every 10°C throughout the test until the sample temperatu re reaches 28°C below the expected flash point and then follow the prescribed dipping procedure. This practice has been shown to reduce the possibility of a fire, and, on average, not to significantly affect the result. A limited study has shown that this dipping practice has no observable effect on test method repeatability.)

When testing materials to determine if volatile material contamination is present, it is not necessary to adhere to the temperature limits for initial ignition source application as stated above in (a) and (b) When testing materials where the expected flash point temperature is not known, bring the material to be tested and the tester to a temperature of 15 + 5°C or 60 + 10°F. NOTE —Flash Point results determined in an “unknown expected flash point mode” should be considered approximate. This value can be used as the expected flash point when a fresh specimen is tested in the standard mode of operation. Record as the observed flash point the reading on the temperature measuring device at the time ignition source application causes a distinct flash in the interior of the test cup. The sample is deemed to have flashed when a large flame appears and instantaneously propagates itself over the entire surface of the test specimen. When the ignition source is a test flame, the application of the test flame may cause a blue halo or an enlarged flame prior to the actual flash point. This is not a flash and shall be

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ignored. When a flash point is detected on the first application, the test shall be discontinued, the result discarded, and the test repeated with a fresh test specimen. The first application of the ignition source with the fresh test specimen shall be 23 + 5°C or 41 + 9°F below the temperature at which a flash point was detected on the first application. When a flash point is detected at a temperature which is greater than 28°C or 50°F above the temperature of the first application of the ignition source, or when a flash point is detected at a temperature which is less than 18°C or 32°F above the temperature of the first application of the ignition source, the result shall be considered approximate, and the test repeated with a fresh test specimen. Adjust the expected flash point for this next test to the temperature of the approximate result. The first application of the ignition source with the fresh test specimen shall be 23 + 5°C or 416 + °F below the temperature at which the approximate result was found. When the apparatus has cooled down to a safe handling temperature, less than 55°C (130°F), remove the test cover and the test cup and clean the apparatus as recommended by the manufacturer. NOTE —Exercise care when cleaning and positioning the lid assembly so not to damage or dislocate the flash detection system or temperature measuring device. See the manufacturer’s instructions for proper care and maintenance. H.7.2 Automated Apparatus: The automated apparatus shall be capable of performing the procedure as described in H.7.1, including control of the heating rate, stirring of the test specimen, application of the ignition source, detection of the flash point, and recording the flash point. H.7.2.1 Start the automated apparatus in accordance with the manufacturer’s instructions. (Warning— Failure to install the sample temperature measuring device correctly, when using automated apparatus, can result in uncontrolled heating of the test portion and potentially a fire. Some automated apparatus include provisions to avoid this occurrence.) The apparatus shall follow the procedural details described in H.7.1 H.8 PROCEDURE B Procedure H.8.1 Manual Apparatus: Fill the test cup with the test specimen to the filling mark inside of the test cup. The temperature of the test cup and test specimen shall be at least 18°C or 32°F below the expected flash point. If too much test specimen has been added to the test cup, remove the excess using a syringe or similar device for withdrawal of fluid. Place the test cover on the test cup and place the assembly into the apparatus. Be sure the locating or locking device is properly engaged. If the temperature measuring device is not already in place, insert the device into its holder. Light the test flame and adjust it to a diameter of 3.2 to 4.8 mm (0.126 to 0.189 in.), or switch on the electric igniter and adjust the intensity in accordance with the manufacturer’s instructions. (Warning— Gas pressure should not be allowed to exceed 3 kPa (12 in.) of water pressure.) (Warning— Exercise care when using a gas test flame. If it should be extinguished it will not ignite the vapors in the test cup and the gas for the test flame that then enters the vapor space can influence the result.) (Warning— The operator should exercise and take appropriate safety precautions during the initial application of the ignition source, since test specimens containing low-flash material may give an abnormally strong flash when the ignition source is first applied.) (Warning— The operator should exercise and take appropriate safety precautions during the performance of these test methods. The temperatures attained during these test methods, up to 370°C (698°F), are considered hazardous.) Turn the stirring device at 250 +10 rpm, stirring in a downward direction. Apply the heat at such a rate that the temperature as indicated by the temperature measuring device increases 1 to 1.6°C (2 to 3°F)/mi n. Proceed as prescribed in H 7, with the exception of the preceding requirements for rates of stirring and heating. H.8.2 Automated Apparatus:

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The automated apparatus shall be capable of performing the procedure as described in H.8.1, including control of the heating rate, stirring of the test specimen, application of the ignition source, detection of the flash point, and recording the flash point. Start the automated apparatus in accordance with the manufacturer’s instructions. The apparatus shall follow the procedural details in accordance with H.8.1 above. H.9 PRECISION, CALCULATION, AND REPORT FOR PROCEDUR ES A AND B H.9.1 Calculation Observe and record the ambient barometric pressure (see Note H 3.5) at the time of the test. When the pressure differs from 101.3 kPa (760 mm Hg), correct the flash point as follows: Corrected flash point C+ 0.25 (101.3 – K) (1) Corrected flash point F + 0.06 (760 – P) (2) Corrected flash point C + 0.033 (760 – P) (3) where: C = observed flash point, °C, F = observed flash point, °F, P = ambient barometric pressure, mm Hg, and K = ambient barometric pressure, kPa. After correction for barometric pressure, round the temperature to the nearest 0.5°C (1°F) and record. H.9.1 Report H.9.1.1 Report the corrected flash point as Procedure A or Procedure B Pensky-Martens Closed Cup Flash Point of the test specimen. H.9.2 Precision and Bias (Procedure A) Precision—The precision of this procedure as determined by the statistical examination of the interlaboratory test results, is as follows: Repeatability—The difference between successive results, obtained by the same operator with the same apparatus under constant operating conditions on identical test material, would in the long run, in the normal and correct operation of the test method, exceed the following values in 1 case in 20. r = AX, (4) A = 0.029, X = mean result in °C, and r = repeatability. Reproducibility—The difference between two single and independent results, obtained by different operators working in different laboratories on identical material, would in the long run, in the normal and correct operation of the test method, exceed the following values only in 1 case in 20. R =BX, (5) B = 0.071, X = mean result in °C, and R = reproducibility. Bias—Since there is no accepted reference material suitable for determining the bias for the procedure in these test methods, bias has not been determined. Relative Bias—Statistical evaluation of the data did not detect any significant difference between the reproducibility variances of manual and automated Pensky-Martens flash point results for the samples studied. Evaluation of the data did not detect any significant difference between averages of manual and automated Pensky-Martens flash point for the samples

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studied with the exception of cycle oil and fuel oil which showed some bias. In any case of dispute, the manual procedure shall be considered the referee test. NOTE —The precision statements were derived on clear liquids only. H.9.3 Precision and Bias (Procedure B) Precision—The precision of this procedure, as determined by the statistical examination of the interlaboratory test results, is as follows: Repeatability—The difference between successive results obtained by the same operator with the same apparatus under constant operating conditions on identical test materials would, in the long run, in the normal and correct operation of the test method, exceed the following value in 1 case in 20: Residual fuel oil 2°C Other types 5°C Reproducibility—The difference between two single and independent results obtained by different operators working in different laboratories on identical material would, in the long run, exceed the following value only in 1 case in 20: Residual fuel oil 6°C Other types 10°C NOTE —The precisions of these standards were derived from interlaboratory studies conducted in the C–scale using C–scale measuring devices. Bias—Since there is no accepted reference material suitable for determining the bias for the procedure in these test methods, bias has not been determined. NOTE —Procedure B was not tested in the 1991 interlaboratory program. H.10 APPARATUS SPECIFICATIONS A typical assembly of the apparatus, gas heated, is shown in Fig. A1.1. The apparatus shall consist of a test cup, cover, and stove conforming to the following requirements: Cup—The cup shall be of brass, or other nonrusting metal of equivalent heat conductivity, and shall conform to the dimensional requirements in Fig. A1.2. The flange shall be equipped with devices for locating the position of the cup in the stove. A handle attached to the flange of the cup is a desirable accessory. The handle shall not be so heavy as to tip over the empty cup. Cover: Cover Proper—The cover shown in Fig. A1.3 shall be of brass and shall have a rim projecting downward almost to the flange of the cup. The rim shall fit the outside of the cup with a clearance not exceeding 0.36 mm (0.014 in.) on the diameter. There shall be a locating or locking device, or both, engaging with a corresponding device on the cup. The four openings in the cover, A, B, C, and D, are shown in Fig. A1.3. The upper edge of the cup shall be in close contact with the inner face of the cover throughout its circumference. Shutter—The cover shall be equipped with a brass shutter (Fig. A1.1 and Fig. A1.4), approximately 2.4 mm (3⁄32 in.) thick, operating on the plane of the upper surface of the cover. The shutter shall be so shaped and mounted that it rotates on the axis of the horizontal center of the cover between two stops, so placed, that when in one extreme position, the

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shutter shall exactly close the three openings. When operated to the other extreme, the three cover openings shall be exactly open and the tip of the exposure tube shall be fully depressed. Flame-Ignition Device—The flame-ignition device (Fig. A1.4) shall have a tip with an opening 0.69 to 0.79 mm (0.027 to 0.031 in.) in diameter. This tip shall be made preferably of stainless steel, although it may be fabricated of other suitable metals. The flame-exposure device shall be equipped with an operating mechanism which, when the shutter is in the open position, depresses the tip so that the center of the orifice is between the planes of the under and upper surfaces of the cover proper at a point on a radius passing through the center of the larger opening A (Fig. A1.3). An electric igniter is also suitable. The electric igniters shall be of the electric resistance (hot-wire) type and shall position the heated section of the igniter in the aperture of the test cover in the same manner as the gas flame device. Pilot Flame—A pilot flame shall be provided for automatic relighting of the exposure flame. A bead 4 mm (5⁄32 in.) in diameter can be mounted on the cover so that the size of the test flame can be regulated by comparison. The tip of the pilot flame shall have an opening the same size as the tip of the flame exposure device (0.69 to 0.79 mm (0.027 to 0.031 in.) in diameter). Stirring Device—The cover shall be equipped with a stirring device (Fig. A1.4) mounted in the center of the cover and carrying two 2-bladed metal propellers. In Fig. A1.4 lower propeller is designated by the letters L, M, and N. This propeller shall measure approximately 38 mm from tip to tip, with each of its two blades 8 mm in width with a pitch of 45°. The upper propeller is designated by the letters A, C, and G. This propeller measures approximately 19 mm, tip to tip, each of its two blades is also 8 mm in width with a pitch of 45°. Both propellers are located on the stirrer shaft in such a manner that, when viewed from the bottom of the stirrer, the blades of one propeller are at 0 and 180° while the blades of the other propeller

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are at 90 and 270°. A stirrer shaft may be coupled to the motor by a flexible shaft or a suitable arrangement of pulleys. Stove—Heat shall be supplied to the cup by means of a properly designed stove which is equivalent to an air bath. The stove shall consist of an air bath and a top plate on which the flange of the cup rests. Air Bath—The air bath shall have a cylindrical interior and shall conform to the dimensional requirements in Fig. A1.1. The air bath may be either a flame or electrically heated metal casting, or an electric-resistance element (H.10). In either case, the air bath must be suitable for use at the temperatures to which it will be subjected without deformation. Heater, Flame or Electric—If the heating element is a flame or an electric heater, it shall be so designed and used that the temperatures of the bottom and the walls are approximately the same. In order that the air bath internal surfaces should be at a uniform temperature, it should not be less than 6.4 mm (1⁄4 in.) in thickness unless the heating element is designed to give equal heat flux densities over all the wall and bottom surfaces. Heater, Electric Resistance—If the heater is of the electric resistance type, it shall be constructed so that all parts of the interior surface are heated uniformly. The wall and bottom of the air bath shall not be less than 6.4 mm (1⁄4 in.) in thickness unless the resistance heating elements are distributed over at least 80 % of the wall and all the bottom of the air bath.A heater having such a distribution of the heating elements positioned at least 4.0 mm (5⁄32 in.) away from the internal surface of the heating unit can be used in conjunction with a minimum thickness of 1.58 mm (1⁄16 in.) for the wall and bottom of the air bath. Top Plate—The top plate shall be of metal, and shall be mounted with an air gap between it and the air bath. It may be attached to the air bath by means of three screws and spacing bushings. The bushings should be of proper thickness to define an air gap of 4.8 mm (3⁄16 in.), and they shall be not more than 9.5 mm (3⁄8 in.) in diameter.

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Annex I Determination of evaporation rate Using a syringe, pour out 0.2 ml of a 50/50 mixture of standard white spirits onto a whatman No.541 filter paper at 20o C and record the time taken for it to evaporate by use of a stop watch. Annex J PRECAUTIONARY STATEMENTS J.1 ACETIC ACID (GLACIAL) Danger — Poison. Corrosive. Combustible. May be fatal if swallowed. Causes severe Burns. Harmful if inhaled. Do not get into eyes, on skin, on clothing. Do not breath vapour, spray, or mist. Dilute by addition of acid to water. Keep away from heat and open flame. Keep in tightly closed container in approved acid storage cabinet. Keep cool. Loosen closure carefully when opening. Use with adequate ventilation. Keep container closed when not in use. Use protective clothing and goggles when handling. Wash thoroughly after handling. J.2 COMPRESSED GASES (HELIUM,NITROGEN AND ARGON) Caution – Compressed gas under high pressure. Gas reduces oxygen available for breathing. Keep container closed. Use with adequate ventilation. Do not enter storage areas unless adequately ventilated. Always use a pressure regulator. Release regulator tension before opening cylinder. Do not transfer to cylinder other than one in which gas is received. Do not mix gases in cylinders. Do not drop cylinder. Make sure cylinder is supported at all times. Stand away from cylinder outlet when opening cylinder valve. Keep cylinder from corrosive environment. Do not use cylinder without label. Do not use dented or damaged cylinder. For technical use only. Do not use for inhalation purpose.

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J.3 ISOOCTANE Danger – Extremely flammable. Harmful if inhaled. Vapour may cause flash fire. Keep away from heat, sparks, and open flame. Keep container closed. Use with adequate ventilation. Avoid build-up of vapours and eliminate all sources of ignition, especially nonexploision proof electrical apparatus and heaters. Avoid prolonged breathing of vapour or spray mist. Avoid prolonged or repeated skin contact. J.4 OXYGEN Warning – Oxygen vigorously accelerates combustion. Keep oil and grease away. Do not use oil/grease on regulators, gauges, or control equipment. Use only with equipment conditioned for oxygen service by carefully cleaning to remove oil, grease and other combustibles. Keep combustibles away from oxygen and eliminate ignition sources. Keep surface clean to prevent ignition or explosion or both, on contact with Oxygen. Always use a pressure regulator. Release regulator tension before opening cylinder valve. All equipment and containers used must be suitable and recommended for oxygen service. Never attempt to transfer oxygen from cylinder in which it is received to any other cylinder. Do not mix gases in cylinders. Do not drop cylinder. Make sure cylinder is secured at all times. Keep cylinder valve closed when not in use. Stand away from outlet when opening cylinder valve. For technical use only. Do not use for inhalation purposes. Keep cylinder from corrosive environment. Do not use cylinder without label. Do not use dented or damaged cylinders. See compressed Gas Association Booklet G-4 and G-4.1 for details of safe practice in the use of oxygen.

KENYA STANDARD WHITE SPIRIT—SPECIFICATION

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Transcript of KENYA STANDARD WHITE SPIRIT—SPECIFICATION