Obtaining Liquid Hydrocarbon

Samples for Analysis by

Gas Chromatography

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Adopted as Tentative Standard, 7974

Adopted as a Standard, 7979
Revised 7983, 7993
Reprinted 7996, 7997, 7998,2000

Gas Processors Association

6526 East 60th Street

Tulsa, Oklahoma 74145

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DISCLAIMER
GPA publications necessarily address problems of a general nature and may be used by anyone desiring to
do so. Every effort has been made by GPA to assure accuracy and reliability of the information contained in
its publications. With respect to particular circumstances, local, state, and federal laws and regulations
should be reviewed. It is not the intent of GPA to assume the duties of employers, manufacturers, or

GPA makes no representation, warranty, or guarantee in connection with this publication and hereby
expressly disclaims any liability or responsibility for loss or damage resulting from its use or for the
violation of any federal, state, or municipal regulation with which this publication may conflict, or for any
infringement of letters of patent regarding apparatus, equipment, or method so covered.

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FOREWORD
This 1993 revision of GPA Publication 2174 is based on the original 2174 publication, first published in
1974 and revised in 1983. It has been expanded and revised to include additional natural gas liquids
sampling procedures. These changes are primarily the result of a cooperative analytical study directed by
Gas Processors Association work group through Technical Committee Section B. Testing was performed ol.
eight (8) potential sampling methods. Ten laboratores and eighteen volunteers were eventually involved in
gathering 320 samples that covered over 7,000 data points. Criteria for an acceptable sampling method
required that it demonstrated minimal variability, was representative of the source, and was user friendly.
Details of the project addressed experimental design, sample collection, logic of the evaluation process, and
statistical analysis; final conclusions were presented in the Proceedings of the Gas Processors Associations
67th Annual Convention, March 1988, in Dallas, Texas.
Sampling methods found to be acceptable from the chromatographic analysis of the 10 common components
of the natural gas liquids and which are covered in the work group report are:
1. Floating Piston Cylinder (original GPA Standard 2174)

2. Water Displacement (total H 20 removal - 80% replaced by hydrocarbons; 20% displaced for outage)
3. Water Displacement (partial H20 removal - 70% replaced by hydrocarbons; 20% displaced for
outage; 10%remaining in cylinder)
4. Ethylene Glycol Displacement (total glycol removal - 80% replaced by hydrocarbons; 20% displaced
for outage)
Proper samples can be obtained when using any of the four methods listed, provided a strict adherence to
detail is maintained. It is recommended that the potential users of these methods study the work group
report prior to selection of an applicable method.

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OBTAINING LIQUID HYDROCARBON SAMPLES FOR ANALYSIS BY GAS

CHROMATOGRAPHY
1. SCOPE

at the bottom. It is suongly recommended that the samples be

obtained under the supervision of a person knowledgeable in the
phase behavior of hydrocarbon systems and experienced in all
sampling operations.

1.1 The specific purpose of this method is to describe the

equipment and procedures for obtaining representative samples
of natural gas liquids and the subsequent preparation of those
samples for laboratory analysis by gas chromatography. The
procedures described in this method may be used for obtaining
samples for analysis by methods other than gas chromatography.
A SAMPLE PROBE MUST BE USED TO OBTAIN A
REPRESENTATIVE SAMPLE.

3.4 The scope of this method does not include

recommendations for the location of the sampling point in a line
or vessel, although the importance of the proper sampling
location cannot be overemphasized.

3.5 A certain amount of information about a sample is

necessary before it can be intelligently handled in the laboratory.
Essential information includes the sample source, sample date,
cylinder identification, sample source pressure and temperature,
ambient temperature, type of analysis required, and the sampling
method used. There may be additional related facts such as
field-determined results and operating conditions which will
assist in the evaluation of the analytical data. This information
must accompany the filed sample cylinder.

2. OUTLINE OF METHODS

2.1 A hydrocarbon fluid sample is transferred under

pressure from a source into a sample container by one of the
following methods:
a. Floating Piston Cylinder Method
b. Water Displacement Method 1 (total H 2 0 removal - 80%
replaced by hydrocarbons; 20% displaced for outage)

3.6 If the hydrocarbon fluid samples are to be transported by

common carrier within the United States, the sample containers
must meet the specifications of and be labeled and packaged
according to the Hazardous Materials Regulations of the
Department of Transportation.

c. Water Displacement Method 2 (partial H20 removal 70% replaced by hydrocarbons; 20% displaced for outage; 10%
remaining in cylinder)
d. Ethylene Glycol Displacement Method (total glycol
removal - 80% replaced by hydrocarbons; 20% displaced for
outage)

NOTE 1: Methods b, c, and d may not be applicable to the analysis

of certain samples containing reactive non-hydrocarbonssuch as sulfur
compounds, carbon dioxide, etc.

3.8 For floating piston cylinders, it is desirable in most

cases to use an "inert" charge gas for the piston cylinder which
is not present in the sample so that a leak in the cylinder itself
can be easily detected during the analysis. The use of natural
gas as a back pressure fluid is not recommended because a leak
across the piston may result in compromising the sample with
hydrocarbons (or other components) which were not actually
present at the source. A method to insure a leak-free cylinder is
to pressure test both sides of the piston cylinder. This is
accomplished by pressurizing the displacement chamber with
inert gas to a typical operating pressure with valve C opened
(see Fig. 1). Next, close valves C and D and note the pressure
reading on gauge N. After a period of five minutes, a decrease
in pressure as indicated at gauge N and a corresponding increase
in pressure at gauge M would indicate a leak across the piston.
A pressure drop only at gauge N indicates a -1
fitting, valve,
gauge, or rupture disc. nie inert gas should be removed from
the displacement end and the above procedure repeated for the
sample side. It is also possible to analyze the inert gas side of

3. GENERAL INFORMATION
3.1 The objective of any sampling operation is u, secure, in
a suitable container, an adequate portion of a hydrocarbon fluid
under pressure, having the same composition as the stream being
sampled.

3.2 Particular emphasis should be given to the necessity of

obtaining accurate, representative samples for analysis since
analyses, regardless of the care and accuracy of the laboratory
tests, may be useless if the samples are not valid.

3.3 It is not possible, nor is it the intent of this method, to

provide a procedure that will be applicable for ail sampling
situations. The sample source here is assumed to be a
homogeneous, single-phase liquid. All samples must be
obtained using a probe designed to secure product from the
center one-third of the flowing stream. The location of the
probe fitting should be on the top or side of the line rather than
3

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3.7 This method assumes all procedures begin with clean,

leak-free sample cylinders. Cylinders must be thoroughly
cleaned prior to sampling with an appropriate volatile solvent or
by following manufacturers' recommendations. The use of
detergenvwater solutions or steam is not recommended for the
cleaning of floating piston cylinders.

SAMPLE
SOURCE

PROBE

R1

I
SAMPLE

FLOATING
PISTON
INERT GAS

CYLINDER

1
N

INDICATOR ROD

Figure 1. Typical Visual Indicator Sampling System

the cylinder to determine hydrocarbon concentration if leakage
occurs in that direction. Cylinders should be tested at least on an
annual basis.

design) may prevent the flashed product from returning to the

original homogeneous mixture.

3.1O Duplicate Samples

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3.9 Care must be exercised when sampling liquids having a

vapor pressure higher than atmospheric pressure to prevent
flashing of lighter components when transferring product from
the source to a sample cylinder, or from a primary sample
cylinder to a secondary cylinder. For floating piston cylinders,
precautions should also be taken to ensure that the inert gas
pressure in the piston cylinder never drops below the sampling
pressure or the products vapor pressure at the existing source
temperature, thus preventing flashing of the sample.
Theoretically, the product in the vapor state could be returned to
liquid phase, but the physical restrictions of the piston cylinder
(e.g., rupture disc, valve dead space, and stirring assembly

3.10.1 When resampling is difficult or impossible, it is

advisable to take duplicate samples as a precaution against
accidental loss. These duplicate samples must be taken using
the same sampling method and from the same sampling location.
The sample sequence should be noted on the sample information
tag.
4. APPARATUS
4.1 Sample Containers

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4.1.1 Floating Piston Cylinders

4.1.1.6 Other types of floating piston cylinders are available
which have no visual method of determining the sample volume
directly. For these cylinders, a displacement cylinder, cylinder
Y (Fig. 2), is fabricated from metal tubing. This cylinder must
be designed to meet the same pressure requirements as the piston
cylinder and have a volume of no more than 80 percent of the
pressurizing volume of the piston cylinder.

4.1.1. I The container required for this method is constructed

of metal tubing, honed and polished on the inside surface. The
cylinder is preferably closed with removable end caps to provide
access to remove and service the moving piston. The end caps
are drilled and tapped for valves, gauges, and relief valves. The
cylinder is designed consistent with the maximum pressure
anticipated during sampling and to be nonreactive to materials
being sampled, the pressurizing fluid, the cleaning solvents and
the expected corrodants. The volume of the cylinder will
depend on the amount of sample needed for the laboratory
analysis.

4.1.2 Double Valve Cylinders

4.1.2.1 Metal sample containers of a type which insure
maximum safety and which are corrosion resistant to the product
being sampled should be used. Stainless steel containers are
recommended to minimize problems of surface adsorption of
heavy components (hexanes and heavier components) and to
minimize the reaction of carbon dioxide or other contaminants
with the container. Sample containers and valves must have a
working pressure equal to or exceeding the maximum pressure
anticipated in sampling, storage, or transportation of the sample
container. Soft-seated valves are preferable to those having
metai-to-metal seats. The size of the container depends upon the
amount of sample required for the laboratory tests to be
performed.

4.1.1.2 The cylinder itself contains a moving piston

equipped with O-rings, teflon rings, or other devices to effect a
leak-free seal between the sample and the pressurizing fluid
while allowing it to move freely within the cylinder. The use of
guide rings is recommended to assure smooth piston travel. The
piston and sealing device must be non-reactive to the sample, the
pressurizing f l u i d , the cleaning solvents, and expected
corrodants.

CAUTION: Some types of lubricating fluids will absorb

appreciable amounts of the c@fraction from the gas being
sampled, thus compromising the integrity of the sample. I t is
recommended that non-absorbing Iubrcating greases, such as,
but not imiled to DuPonts Krytox AC or AD, be used to prevent
this difficulty. Further details regarding non-absorbing
lubricating greases can be obtained from the piston cylinder
manufacturers.

NOTE 2: DOT regulations regarding the use of pressure relief

devices on these cylinders must be followed.

4.2 Sample Transfer System

4.2.1 Transfer lines, valves, and gauges in the transfer
system shall be designed consistent with maximum anticipated
pressure and be resistant to ail expected corrodants. (Stainless
steel is preferred.) The transfer lines should have a minimum
diameter of 1/4 inch (6.35 mm) and be as short as is practical.
The use of filters and dryers is discouraged.

4.1.1.3 All valves and safety devices must meet the

appropriate material and pressure requirements for safe design.
The pressure reliefs may be of spring or rupture disc types.
These allow a partial or complete loss of contents due to thermal
expansion or over-pressurization. Should relieving occur, the
sample should be considered compromised.

4.3 Composite Sampling Mechanism

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4.3.1 A composite sampling mechanism is a device which is

used to obtain a representative sample from a flowing product
stream over a given period of time. The unit consists of a
sample probe, either a flow-through sample injection valve,
whether automatic or manual (see Figures 3 and 4) or a probemounted sample pump (Fig. 5) and utilizes a floating piston
cylinder as its collection chamber. The system must include a
method to mix the product sample in the collection chamber.
This is necessary regardless of whether the original floating
piston cylinder is removed and used for laboratory analysis or a
transfer of the product sample is made into a secondary cylinder
as described herein. (Figure 6 depicts a typical automatic
sampler and the various parts required. Figure 5 depicts a
typical proportional sampler using an injection pump and the
various parts required.)

4.1.1.4 Some piston-type cylinders are fabricated from nonmagnetic materials such as the 300 series stainless steel. The
piston likewise is fabricated of stainless steel but has magnets
attached to the precharge side of the piston. As the piston moves
the length of the cylinder, the magnetic field generated by the
magnets flips a series of bi-colored flags. This system, or
systems of similar configuration, indicates the piston position
and the volume of product in the cylinder.

4.1.1.5 Some piston-type cylinders are fabricated with a rod

attached to the piston which extends through the end cap on the
inert gas back pressure chamber with appropriate sealing devices
to prevent the inert gas from leaking. The traveling rod provides
an indication of the piston position and the volume of the
product sample in the cylinder. Again, some variations of this
style may exist.

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SAMPLE

SOURCE

PROBE

R1

SAMPLE

PlSTON

INERT GAS
M!NOER

AIR

Figure 2. Displacement Cylinder Sampling System

5. SAMPLING PROCEDURES

4.4 Sample Filters

5.1 Floating Piston Cylinder Method

4.4.1 The sample filter is an optional device used to protect

the sampling valve from scoring due to the presence of foreign
contaminants such as metal shavings, dirt, etc., in a NGL
sample. The filter should be of a small total volume, of an
inline-type design, and contain a replaceableldisposable element.

5.1.1 Technique of using a cylinder equipped with visual

indicator for liquid phase samples of spofor instantaneous
type (see Figure 1)

5.1.1.1 With sample side of cylinder evacuated (from

cleaning operation) and valve C open, fill displacement end with
inert gas to a pressure at least 10 psi (69 kPa) above sampling
pressure. Close valve D.

CAUTION; A filter may introduce error if nof handled

properly. The filter should be clean and free of any residual
product from previous samples so that a buildup of heavy-end
hydrocarbon components does not result. (This may be
accomplished by a heatinglcooling process or inert gas purge,
etc.) The filter element should be 15 micron size or larger so
that during the purging process NGL is not flashed, causing
fractionation and bubble formation.

5.1.1.2 Open valve A at sample source and thoroughly blow

out any accumulated materiai. Close valve A at sample source.
.~

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PRESSURE)

Not for Resale

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PNP ( 5 i 0 10 PSI AP)

'

Figure 4. Typical Sample Probe Installation

for a Pump

5.1.1.3 Connect piston cylinder to sampling source at

valve A.

5.1.1.8 Close valves D, C, and A in that order. Open valve

B to release pressure on the sample line. Disconnect the
cylinder from sample source.

5.1.1.4 With valves B and C closed, open source valve A to

full open position. Observe sample pressure on gauge L. Crack
valve B and fitting at valve C to purge line. Do not allow
pressure L to drop below original sample pressure. Discontinue
purging after a sufficient time and only when liquid product is
present. If the product flashes without leaving a liquid residue at
valve B and the fitting at valve C, the operator must use
judgment in determining when to discontinue purging. Close
valve B and tighten fitting at valve C.

5.1.1.9 Do not take outage or reduce pressure on piston

cylinder. Check valves C and D for leaks, cap valves to protect
threads, prepare sample information tag and box for
transportation as per Department of Transportation or applicable
requirements.
5.1.2 Technique of using cylinder not equipped with visual
indicator for liquid phase samples, via displacement cylinder, of
"spot" or "instantaneous" type (see Figure 2 )

NOTE 3: If the diameter of the indicator rod is of significant size

compared to the piston, then the pressure on the inert gas side will be
slightly higher than the sample side, i.e.. gauge N will read higher than
gauges L and M. This comment applies to all subsequent comments
regarding equal pressures on gauges L, M and N.

5.1.2.1 With sample side of the piston cylinder evacuated

(from cleaning operation) and valve C open, fill displacement
end with inert gas to a pressure at least 10 psi (69 P a ) above
sampling pressure. Close valve D.

5.1.1.5 Adjust pressure on gauge N to equal pressure L by

releasing adequate inert gas through valve D.

5.1.2.2 Open valve A at sample source and thoroughly blow

out any accumulated material. Close valve A at sample source.

5.1.1.6 With valve D closed, slowly open valve C

completely. There should be no pressure change on gauge N
and pressure at gauges L, M and N should all be equal.

5.1.2.3 Connect piston cylinder X to sample source at valve

A and displacement cylinder Y to piston cylinder. Displacement
cylinder Y should be filed with air at atmospheric pressure. For
proper cylinder sizing refer to Section 4.1.1.6.

5.1.1.7 Partially open valve D, slowly allowing inert gas to

vent to the atmosphere. To prevent flashing, do not allow
pressure M to drop below sampling pressure. Continue the
operation until the indicator designates the cylinder contains
80% by volume of product (folIowing manufacturer's
instructions).

5.1.2.4 With valves B and C closed, open sample source

valve A to full open position. Observe sample source pressure
on gauge L. Crack valve B and fitting at valve C to purge line.
Do not allow pressure L to drop below originai sample pressure.

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Figure 3. Typical Sample Probe Installation

on Orifice Flange

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Product
flow

tvlinimum
5 Diameters

injection pump

Pulse
divider
circuit

tubing

Pressure

f
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- Inert

Pressure
supply

gas

Check valve

Sample transfer tap

Bleed valve

Figure 5. Typical Proportional Sampler Using an Injection Pump

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3
y

1 PPB

PULSE
DIVIDER
1 PULSE PER

"X' BBLS.

AC

INJECTION VALVE

-----

r
,

I
I
PRESSURE
RECORDER

TUBING 1 - 1

INERT GAS
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PISTON
SAMPLE

aWPLE

TRANSFER TAP
VALVE

I
I

PRESSURE
SUPPLY
SAMPLE MIXING DEVICE

Figure 6. Typical Automatic Proportional Sampler

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Discontinue purging after a sufficient time and only when liquid

product is present. If the product flashes without leaving a
liquid residue at valve B and the fitting at valve C, the operator
must use judgment in determining when to discontinue purging.
Close valve B and tighten fitting at valve C.

5.1.3.4 All samples must be obtained using a probe. (Refer

to Section 3.3 for specifications and location.) A bypass device
that causes a differential pressure, such as an orifice plate or p .
small pump, is used to supply fresh liquid to a location fc
filling the sample container, either manually or by use of sample
injection valves. The bypass sample line utilizes short lines of a
small diameter connecting the fresh sample source to the
floating piston cylinder receiver (see Figures 3 and 4).
5.1.3.5 The floating piston cylinder should be connected to
the purged sample line via the composite sampling device. Inert
gas pressure or appropriate pressurizing fluid should be applied
to the cylinder to force the piston to the starting end of the
sampling cylinder. The inert gas pressure should be maintained
at a pressure which exceeds by 200 psi (1379 kPa) the
equilibrium vapor pressure of the fluid sampled under expected
varying temperature conditions. At pressure differences less
than 200 psi (1379 kPa) the chance for erroneous samples
increases.

5.1.2.6 With valve E closed, slowly open valve C to full

open position. There should be no pressure change indicated on
gauge N and pressure at gauges L, M and N should all be equal.
5.1.2.7 Close valve D. Open valve E and properly vent
pressure through valve F. Close valve F.
5.1.2.8 Slowly open valve D, allowing inert gas from
cylinder X to flow into cylinder Y . Observe gauge M so as not
to allow pressure M to drop. Continue operation until pressure
of all three gauges equalizes. At this point, a volume equal to
cylinder Y has been displaced into cylinder X by the product
sample. Sample cylinder X now contains 80% by volume of
sample, leaving sufficient inert gas space to insure safe storage
and transport.

5.1.3.6 The automatic sample injection valves will require

adjusting to obtain incremental samples at a rate such that the
floating piston cylinder will have adequate capacity to hold the
sample during its period of sampling. Care should be exercised
to prevent overfilling of the sample container so that relieving
does not occur, thus changing the composition of the sample and
creating a serious safety hazard.

5.1.2.9 Close valves D, C , and A in that order. Open valves

B and F. Disconnect displacement cylinder Y . Disconnect
piston cylinder X from sample source.

5.1.3.7 Increasing or decreasing the volume of sampl

desired can be accomplished by changing the volume of the
incremental sample obtained with the injection valve and/or by
changing the frequency of the proportioning device which
controls the injection valve.

5.1.2.10 Do not take outage or reduce pressure on piston

cylinder X. Check valves C and D for leaks, cap valves to
protect threads, and prepare sample information tag and box for
transport as per Department of Transportation or applicable
requirements.

5.1.3.8 The sample obtained by the sampler apparatus and

stored in the floating piston cylinder must be mixed thoroughly
by either a mechanical device or a liquid pump and circulating
system.

5.1.3 Technique of using floating piston cylindersfor liquid

phase samples of composite type via manual or automatic
systems (see Figures 5 and 6)

5.1.3.9 The floating piston cylinder used in the above

system may be removed from the composite sampling device
after the desired product has been sampled.

5.1.3.1 Automatic proportional samplers take small samples

of the flowing stream proportional to the flow rate. Time
increments may be used only when the flow rate is constant.

CAUTIONi Under no circumstances should the cylinder be

filled beyond 80% of its capacity with sample.

5.1.3.2 Thorough purging of sample lines, pumps and

connections to the sample cylinder is necessary to avoid
contamination of the sample. Sampler systems should be
designed to minimize stagnant areas which could result in the
sample not being representative of the fluid source.

5.1.3.10 Do not take outage or reduce pressure on the

cylinder. Check valves for leaks, cap valves to protect threads,
and prepare sample information tag and box for transpon as per
Department of Transportation or applicable requirements.

5.1.3.3 Precautions shall be taken to avoid vaporization in

sample loop lines when operating near the equilibrium pressure
of the liquid. In some instances, it may be necessary to insulate
the sample line and sample container, or control the pressure or
temperature of sample containers containing volatile materiais.

5.1.3.11 If it is not possible to disconnect the primary

floating piston cylinder from the automatic system, the sample
may be transferred to a secondary floating piston cylinder. Once
the sample in the primary cylinder is adequately mixed, proceec

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<

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5.1.2.5 With valve E closed, open valve D and observe

pressure on gauge N. Adjust pressure N to equal pressure L by
slowly venting inert gas through valve E. Close valve E.

Not for Resale

..

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as in step 5.1.1, treating the primary cylinder as a flowing

source. (In this particular transfer situation, as sample is
withdrawn, the master sample container will partially
depressurize. The product vapor pressure at the existing master
sampler temperature must be maintained or exceeded to prevent
flashing.)

5.2 Water Displacement and Ethylene Glycol Displacement

Methods - Total displacement

5.2.1 A double valve sample cylinder filled with clean

ethylene glycol or water and a vessel to measure the displaced
liquid are required for these two methods (see Figure 7).

Ethylene glycol must be the glycol type used. Water must have
a pH between 5.0 and 7.0. Water with a pH greater than 7.0
must be acidified to bring the pH within the proper range. (0.1
N H2SO4 is a satisfactory acid solution.)

5.2.2 The total volume of the sample cylinder must be

found, then 80% of the total volume should be calculated. (For
example, if the total volume of the cylinder is 500 ml, then 80%
of the total volume is 400 mi.)
5.2.3 Open valve A at sample source and thoroughly blow
out any accumulated material. Close valve A at sample source.

SAMPLE

SOURCE

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Figure 7. Liquid Displacement Sampling

/

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5.2.4 Connect the sample cylinder to sampling source at

valve A exactly as shown in Figure 7.

5.3.3 Open valve A at sample source and thoroughly blow

out any accumulated material. Close valve A at sample source.

5.2.5 With valves B, C, and D closed, open sample source

valve A to full open position. Observe sample pressure on
gauge L. Crack valve B and fitting at valve C to purge line. Do
not allow pressure L to drop below original sample pressure.
Discontinue purging after a sufficient time and only when liquid
product is present. If the product flashes without leaving a
liquid residuc at valve B and the fitting at valve C, the operator
must use his judgement in determining when to discontinue
purging. Close valve B and tighten fitting at valve C .

5.3.4 Connect the sample cylinder to sampling source

valve A exactly as shown in Figure 7.
5.3.5 With valves B, C, and D closed, open sample source
valve A to full open position. Observe sample pressure on
gauge L. Crack valve B and fitting at valve C to purge line. Do
not allow pressure L to drop below original sample pressure.
Discontinue purging after a sufficient time and only when liquid
product is present. If the product flashes without leaving a
liquid residue at valve B and the fitting at valve C, the operator
must use his judgement in determining when to discontinue
purging. Close valve B and tighten fitting at valve C.

5.2.6 With valve D still closed, slowly open valve C to full

open position. Pressure at gauges L and M should be equal.

5.3.6 With valve D still closed, slowly open valve C to full

open position. Pressure at gauges L and M should be equal.

5.2.7 Slowly open valve D to allow a slow discharge of the

glycol or water displacement liquid into the measuring vessel.
To prevent flashing, do not allow pressure M to drop below
sampling pressure. Continue operation until 80% by volume of
the displacement liquid has been displaced by product in the
sample cylinder.

5.3.7 Slowly open valve D to allow a slow discharge of thc

water into the measuring vessel. To prevent flashing, do not
allow pressure M to drop below sampling pressure. Continue
operation until 70% by volume of water has been displaced by
product in the sample cylinder.

5.2.8 Close valves D, C and A in that order. Open valve B

to release pressure on sample line.
--`````-`-`,,`,,`,`,,`---

5.3.8 Close valves D, C, and ,A in that order. Open valve B

to release pressure on sample line.

5.2.9 With sample cylinder still attached to source valve A,

slowly open valve D to drain the remaining 20% displacement
liquid from the sample cylinder. After 15 ml has been
withdrawn, the operator should reduce the drain rate and
carefully extract t h e remaining water or glycol. (The
displacement liquid may become cloudy just prior to the end
point, although the effect is less noticeable with glycol.) At this
timc, reduce the rate to 10 ml/min maximum. When the first
indication of product appears, usually a flashing bubble, close
valve D immediately with no further loss of product.
Disconnect cylinder from sample source.

5.3.9 With sample cylinder still attached to source valve /

slowly open valve D to drain another 20% of the water from th,
sample cylinder. (At this point, 10% of the water still remains in
the sample cylinder.) Disconnect sample cylinder from sample
source.

5.3.10 Check valves C and D for leaks, cap valves to protect

threads, prepare sample information tag and box for
transportation as per Department of Transportation or applicable
requirements.

5.2.10 Check valves C and D for leaks, cap valves to protect

threads, prepare sample information tag and box for
transportation as per Department of Transportation or applicable
requirements.

6. LIQUID PHASE LABORATORY HANDLING AND

PREPARATION

6.1 Recommended Procedures for Liquid Phase Samples

Prior to Injection of the Sample into the Test Device

5.3 Water Displacement Method - Partial Displacement

6.1.1 Floating Piston Cylinders

5.3.1 A double valve sample cylinder filled with clean water

and a vessel to measure the displaced liquid are required for this
method (see Figure 7). The water used must meet the same
requirements as in 5.2.1.

6.1.1.1 For floating piston cylinders refer to Figure 8 and

proceed as follows: Connect a source of inert gas to valve A so
that pressure may be applied to the sample via the floating
piston. Apply a pressure not less than 200 psi (1379 Wa) above
the vapor pressure of the sample at the temperature of the
sample injection valve by opening the valve on the inert gas
source and valve A. The inert gas pressure is to be maintained

5.3.2 The total volume of the sample cylinder must be

found; then 70% and 20% of the total volume should be
calculated. (For example, if the total volume of the cylinder is
500 ml, then 70% of the total volume is 350 ml and 20% is 100
mi.)
12
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on the sample container at all times during the analysis via a

precharge regulator or similar device.
6.1.1.2 The sample should be thoroughly mixed per the
cylinder manufacturers recommendations, whether it be by
mixing dasher, mixing ball or equivalent, immediately prior
to each analysis.
6.1.1.3 Connect the sample end of the cylinder, valve B, to
the inlet of the chromatograph liquid sample valve. All
connections and tubing are to be made of material impervious to
the sample composition with the smallest diameter and shortest
length of plumbing practical, thereby minimizing dead space.
All tubing between the sample cylinder and liquid sample valve
should be the same diameter.
6.1.1.4 With valve C closed, open valve B to fill the sample
valve and associated lines.
6.1.1.5 Slowly crack valve C to purge the sample valve and
associated lines. Be sure sufficient volume is displaced to purge
unmixed areas in the sample cylinder as well as the sample
injection system. When the purge is complete, close valve C.

CAUTION: Extreme care must be used to ensure that no

flashing of sample occurs in [he inlet sampling line and valve
system. Any measurements should be taken at sample purge
valve C, never at sample valve B . The sample line and valve
system should remain at 200 psi (1379 W a ) above the vapor
pressure of the product.
6.1.1.6 Operate the liquid sample valve either manually or
automatically to inject the liquid sample into the carrier gas flow
immediately ahead of the chromatographic column. The sample
injection valve should be actuated quickly and smoothly to place
the sample onto the column all at once and to ensure continuous
carrier gas flow through the column.
6.1.1.7 When sample injection is complete, close valves B
and A in that order, then close valve on inert gas source. Slowly
open valve C and vent any remaining unused sample in the
system through an appropriate vent.
6.1.1.8 Disconnect the cylinder from the inlet of the
chromatograph liquid sample valve and the inert gas source.
6.1.1.9 If the sample is to be reused, do not take an outage

CARRIER

CARRIER GAS
TO COLUMN

FLOATING PISTON
PRESSURE
CYLINDER
NEEDLE VALVE

OUTLET VALVE

VENT V A L X

GAS

RELIEF
VALVE

GAS

Figure 8. Repressuring System and ChromatographValving with Floating Piston

13
--`````-`-`,,`,,`,`,,`---

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No reproduction or networking permitted without license from IHS

Not for Resale

//^:^^#^~^^""~:""~#*^~@^"#:$@"^@^":"~:~:^::#^^*^~@^~:\\

CHROMATOGRAPH
LIQUID SAMPLING

or reduce pressure on the piston cylinder. Check valves for

leaks, cap valves to protect threads, and store the cylinder in a
suitable location.
6.1.2 Double Valve Cylinders

--`````-`-`,,`,,`,`,,`---

6.1.2.1 For double valve displacement cylinders, refer to

Figure 9 and proceed as follows: Connect the sample cylinder Y
to cylinder X so pressurizing fluid can enter into the bottom of
cylinder Y. (The pressurizing fluid should be same type used to
secure the product.) With this configuration the hydrocarbon
sample will be taken from the upper portion of the cylinder.
Open valve A and pressurize cylinder X with inert gas.
Maintain a pressure at least 200 psi (1379 kPa) above the vapor

pressure of the hydrocarbon sample at operating conditions.

Open valves B and C to admit pressurizing fluid into sample
cylinder Y.
F
6.1.2.2 Mix the sample thoroughly by gently inverting
cylinder Y several times. Fix cylinder Y in a vertical position by
means of a ringstand or similar device. Allow it to remain
immobile in the vertical position at least 2 minutes before
injection of sample into the chromatograph.
6.1.2.3 Connect the sample outlet valve D on cylinder Y to
the inlet of t h e chromatograph liquid sample valve. Ali
connections and tubing are to be made of matenal impervious to
the sample composition, utilizing the smallest diameter and

CHROUATOGRAPH
LIPUID SAMPLING

VENT VALVE

TO COLUMN

"1

//^:^^#^~^^""~:""~#*^~@^"#:$@"^@^":"~:~:^::#^^*^~@^~:\\

+
o

"f

Figure 9. Repressuring System and Chromatograph Valving with Double Valve Displacement Cylinder

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E.

shortest length of plumbing practical, thereby minimizing dead

space. All tubing between the sample cylinder and liquid
sample valve should be the same diameter.

6.1.2.10 Check the valves for leaks, then cap valves to

protect the threads and store the cylinder in a suitable location.
7. SAFETY PRECAUTIONS

6.1.2.4 With valve E closed, open valve D to fill the sample

valve and associated lines.

CAUTION: Extreme care must be used to ensure that no

flashing of sample occurs in the inlef sampling line and valve
system. Any measurements should be taken at sample purge
valve E , never at sample valve D. The sample line and valve
system should remain at 200 psi (1379 kPa) above the vapor
pressure of the product.
6.1.2.6 Operate the liquid sample valve either manually or
automatically to inject the liquid sample into the carrier gas flow
immediately ahead of the chromatographic column. The liquid
sample valve should be actuated quickly and smoothly to place
the sample onto the column all at once and to ensure continuous
carrier gas flow through the column.

7.2 In all cases, a 20% (or more) inert gas charge should be
present in all floating piston cylinders and a minimum of 20%
displacement fluid outage in all double valve sample cylinders.
7.3 Disassembly of the Piston Cylinder
CAUTIO& Disassembly of the piston cylinder f o r
maintenance requires special precautions. If either end cap is
removed while pressure is on the cylinder, the end caps and the
piston can be ejected with such a force as to cause serious injury
to personnel and damage to adjacent equipment.
7.3.1 Clamp the piston cylinder firmly to a steady work
surface. Caution should be taken not to dent or bend the
cylinder by applying excessive pressure.

6.1.2.7 When sample injection is complete, close valves D

and C on cylinder Y and valves B and A on cylinder X, in that
order, then close the valve on the inert gas source. Slowly open
valve E and vent any remaining unused sample in the system
through an appropriate vent. (If the sample is LO be reused
immediately, do not take an outage or reduce pressure on the
sample cylinder. If the sample is not to be reused immediately,
proceed to next step, 6.1.2.8.)

7.3.2 Using a suitable venting apparatus (e.g. vent hood),

properly vent both ends of the cylinder before attempting to
remove either end cap.

--`````-`-`,,`,,`,`,,`---

//^:^^#^~^^""~:""~#*^~@^"#:$@"^@^":"~:~:^::#^^*^~@^~:\\

6.1.2.5 Slowly crack valve E to purge the sample valve.

When the purge is complete close valve E.

7.1 Sampling hydrocarbon fluids can be hazardous. Persons

responsible for obtaining samples should be familiar with and
adhere to safe practices for handling flammable fluids under
pressure.

7.3.3 The work surface at either end of the cylinder should

be clear before the end plug is loosened.
7.3.4 Provide a mechanical plunger to dislodge the piston
from the cylinders, provided the plunger is of suitable material
as to not scratch the cylinder bore. Do not use fluid pressure to
dislodge the piston.

6.1.2.8 Disconnect cylinder Y from the inlet of the

chromatograph liquid sample valve and disconnect from
cylinder X. Disconnect Cylinder X from the inert gas source.
6.1.2.9 With cylinder Y remaining in the upright position,
remove 20% by volume of the pressurizing fluid for outage.
This is accomplished by slowly opening valve C to allow a slow
discharge of the pressurizing fluid into a measuring vessel.

NOTE 4: For reproducible sample volume limits see GPA

publication 2177.

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No reproduction or networking permitted without license from IHS

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