Gpa STD 2177-2013

GPA Standard 2177-13
Analysis of Natural Gas Liquid Mixtures Containing Nitrogen and

Carbon Dioxide by Gas Chromatography
Adopted as Tentative Standard. 1977

Revised and Adopted as a Standard. 1984
Revised 1989, 1995, 2003, 2012, 2013
Gas Processors Association

6526 East 60th Street
Tulsa, Oklahoma 74145
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Copyright Gas Processors Association

Provided by IHS under license with GPA Licensee=University of Alberta/5966844001, User=trert, rtyrtyrty
No reproduction or networking permitted without license from IHS Not for Resale, 03/04/2015 09:55:59 MST
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 suppliers to warn and
properly train employees, or others exposed, concerning health and safety risks or precautions.
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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FOREWARD
GPA 2177 provides the gas processing industry a method for determining the compositional analysis of
demethanized liquid hydrocarbon streams containing nitrogen, air and carbon dioxide. Purity products such as an
ethane/propane mix and other products that meet the compositional ranges listed in the standard may also utilize this
method.
The precision statements contained in this standard are based on the statistical analysis of round-robin laboratory
data obtained by GPA Section B. The detail of how this data yielded the equations covered in the precisions
statements can be found in GPA RR188.
This standard was developed by the cooperative efforts of many individuals from industry under the sponsorship of
GPA Section B, Analysis and Test Methods.
Throughout this publication, the latest appropriate GPA Standards are referenced.
“Copyright© 2013 by Gas Processors Association. All rights reserved.

No part of this Report may be reproduced without the written consent
of the Gas Processors Association.”
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Analysis of Natural Gas Liquid Mixtures Containing Nitrogen and
Carbon Dioxide by Gas Chromatography
1. SCOPE 2. SUMMARY OF METHOD
1.1 This method is intended for the analysis of 2.1 Components to be determined in a demethanized
demethanized liquid hydrocarbon streams containing hydrocarbon liquid mixture are physically separated by
nitrogen/air and carbon dioxide, and purity products such gas chromatography and compared to calibration data. A
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as an ethane/propane mix that fall within the fixed volume of sample in the liquid phase is isolated in a
suitable sample inlet system and flashed onto the
compositional ranges listed in Table I. This method is
chromatographic column.
limited to mixtures containing less than 5 mole percent of
heptanes and heavier fractions (20 mole percent of
hexanes and heavier fractions). NOTE 4 – For lab chromatographs, the comparison
to calibration data is performed under identical operating
conditions. For on-line chromatographs, the sample may
Table I Components and Recommended not necessarily be at the same conditions as the
Compositional Ranges calibrations data so care should be taken to ensure that
the pressure at the sample injection point is sufficiently
Concentration above the vapor pressure of the product.
Components Range (mole %)
Nitrogen 0.01 – 5.0 2.2 A precut column is backflushed when n-hexane
Carbon Dioxide 0.01 – 5.0 has eluted into the main analytical column, so that the
Methane 0.01 – 5.0 heptanes+ are eluted as a single peak at the beginning of
Ethane 0.01 – 95.0 the chromatogram. Two advantages of this method are:
Propane 0.01 – 100.0 (1) Better precision in measuring the C7+ portion of the
Iso-Butane 0.01 – 100.0 sample, and (2) Reduction in analysis time over the single
N-Butane and 2,2-Dimethylpropane 0.01 – 100.0 column approach by approximately 40%. See Figure 1.
Iso-Pentane 0.01 – 15.0
N-Pentane 0.01 – 15.0
2,2-Dimethylbutane, 2,2-Dimethylbutane, 2.2.1 As an alternate method, the components
and 2-Methylpentane, 3-Methylpentane, 0.01 – 15.0 nitrogen/air through n-hexane are individually separated
Cyclopentane, N-Hexane with the carrier flow in the forward direction. The
Heptanes & Heavier 0.01 – 5.0 numerous heavy end components are grouped into an
irregular shaped peak by reversing direction of carrier gas
through the column via a switching valve immediately
1.2 The heptanes and heavier fraction if present in
following the elution of normal hexane. (See Figure 2.)
the sample is analyzed by either (1) use of a pre-cut Samples which contain no heptanes+ fraction are analyzed
column to elute heptanes and heavier first as a single until the final component has eluted with no reverse of
peak, or (2) reverse flow of carrier gas after n-hexane, and carrier flow.
peak grouping of the heptanes plus fraction. For purity
mixes without heptanes and heavier, no reverse of carrier 2.3 The chromatogram is interpreted by comparing
flow is required. the areas of component peaks obtained from the unknown
sample with corresponding areas obtained from a run of a
NOTE 1 – This method can be used for a hexanes selected reference standard. Any component in the
plus analysis by adjusting the timing of the backflush unknown suspected to be outside the linearity range of the
event to occur following the elution of n-pentane. detector, with reference to the known amount of that
component in the reference standard, must be determined
by a response curve. (See Sections 5.1 & 5.1.1 for further
NOTE 2 – CAUTION: In the case of unknown explanation of instrument linearity check procedures.)
samples with a relatively large C6+ or C7+ fraction and
where precise results are important, it is desirable to
determine the molecular weight (or other pertinent 3. APPARATUS
physical properties) of these fractions. Since this method
makes no provision for determining physical Properties, 3.1 Any gas chromatograph may be used which meet
the physical properties needed must be determined by the criteria listed in Section 8, Precision. The following
extended analysis or agreed to by the contracting parties. equipment specifications have been found useful in
The extended analysis will be made according to GPA designing an instrument to meet those criteria.
Publication 2186.
NOTE 3 – For samples containing more than 5 mole 3.1.1 Environment - The gas chromatograph shall be
percent of heptanes and heavier fractions (20 mole housed in a climate controlled environment to ensure
percent of hexanes and heavier fractions), analysis will be stability.
made according to GPA Publication 2103.
1
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Figure 1 Chromatogram of a Demethanized Hydrocarbon Liquid Mixture. (Frontal Carrier Gas Flow
Through N-Hexane, with Precut of Heptanes Plus).
Figure 2 Chromatogram of Demethanized Hydrocarbon Liquid Mixture. (Frontal Carrier Gas Flow
through N-Hexane with backflush of Heptanes Plus).
3.1.2 Detector - The detector shall be a thermal temperature, and flashing this fixed volume into the
conductivity type. It must be sufficiently sensitive to carrier gas stream ahead of the analyzing column. A
produce a detectable peak for each component of interest metering valve downstream of the liquid sampling valve is
at 100 ppm molar volume. required to maintain the sample as a single phase liquid
through the entire sample inlet system. (See Valve C in
Figure 3.) The fixed sample volume should not be of such
3.1.3 Sample Inlet System. Liquid - A liquid sampling
volume as to impact instrument linearity and should be
valve must be provided, capable of entrapping a fixed
repeatable so that successive runs agree within ± 1% on
volume of sample at a pressure at least 200 psi (1379 kPa)
each component peak area. The liquid sampling valve
above the vapor pressure of the sample at valve
should be mounted exterior of any type heated
2
Figure 3 Pre-Cut Valve Configuration.
compartment and thus be operated at laboratory ambient 3.1.6 Carrier Gas System – Components of the
conditions. A sample filter is an optional device to protect carrier gas system must provide the ability to control the
the liquid sampling valve from scoring due to the presence pressure and/or flow stable enough to achieve the
of foreign contaminants such as metal shavings, dirt, etc., precision requirements in Section 8. It is desirable to use
in an NGL sample. The filter should be of a small total a carrier gas which contains minimal quantities of critical
volume, of an inline type design and contain a impurities (i.e. oxygen, water, and total hydrocarbons).
replaceable/disposable element.
3.2 Integration Systems – Integration software
NOTE 5 – CAUTION: A filter may introduce error if packages offer numerous options regarding peak
not handled properly. The filter should be clean and free interpretation. Users are advised to optimize integration
of any residual product from previous samples so that a prior to calibration and subsequent unknown sample runs.
build up of heavy end hydrocarbon components does not After each analysis is completed the integration should be
result. (This may be accomplished by a heating/cooling verified.
process or inert gas purge, etc.) The filter element should
be 15 micron size or larger so that during the purging
3. Sample Containers
process NGL is not flashed, preventing fractionation and
bubble formation.
3.3.1 Floating Piston Cylinder - A strongly preferred
and recommended device suitable for securing, containing
3.1.4 Chromatographic Columns
and transferring samples into a liquid sample valve and
which preserves the integrity of the sample. (For proper
3.1.4.1 Column No. 1 (Analytical Column) - A operation refer to GPA 2174.) These cylinders must have
partition column must be provided capable of separating an acceptable mixing device.
nitrogen/air, carbon dioxide and the hydrocarbons
methane through normal hexane. (See Figures 1 and 2.)
3.3.2 Double Valve Displacement Cylinder - An
Separation of carbon dioxide must be sufficient so that a
alternate device, used in the absence of a Floating Piston
sample containing 0.01 mole percent carbon dioxide will
Cylinder, suitable for securing, containing and transferring
produce a detectable peak on the chromatogram. (The
samples into a liquid sample valve. (For proper operation
Silicone 200/500 column, containing a 27-30 weight
refer to ASTM D-1265.)
percent liquid phase load, has proven satisfactory for this
type of analysis.) (See Paragraph B-2, Appendix B, GPA
Publication 2261 for further explanation and construction NOTE 6 – CAUTION: This container is ONLY
of column.) acceptable when the displacement liquid does not
appreciably affect the composition of the sample of
interest. Specifically, components such as CO2 or
3.1.4.2 Column No. 2 (Precut Column) – A partition
aromatic hydrocarbons are partially soluble in many
column similar to column No. 1, it must be of the same
displacement liquids and thus may compromise the final
diameter as column No. 1. The column must be of an
analysis. This caution is of the utmost importance and
appropriate length to clearly separate the heptanes plus
should be investigated prior to utilizing this technique.
fraction from the hexanes and lighter components.
3.1.5 Temperature Control – The chromatographic

column(s) and the detector shall be maintained at
temperatures stable enough to achieve the precision
requirements in Section 8.
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3
4. ANALYSIS PROCEDURE flow minus the retention time for the air peak. Only after
baseline is re-established should the run be terminated and
4.1 General - In the routine analysis of samples carrier now returned to original direction.
described in the scope of this procedure, it is possible to
obtain all components of interest from a single run.
Response factors, on a selected reference standard, are 5. CALIBRATION RUN
used to convert peak areas of the unknown sample to
liquid volume percent (mole percent or weight percent are 5.1 In conjunction with a calibration on any specific
acceptable). chromatograph, the linear range of the components of
interest MUST be determined. The linearity should be
4.2 Introduction of Sample – The procedures for established for any new chromatograph and re-established
connecting and introducing a sample either via floating whenever the instrument has undergone a major change
piston cylinder or a double valve displacement cylinder (i.e. replaced detectors, increased sample size, switched
are defined in GPA 2198. column size, or dramatically modified run parameters).
4.3 Precut (or Backflush) Valve Switching 5.1.1 This method utilizes gravimetrically prepared
standards of a higher concentration than is contained in
4.3.1 The use of a pre-cut column to group the C7+ the unknown. A set of response factors is first determined
fraction at the beginning of the chromatogram as a single for all components via a blend mix. (See Section 5.3.) A
peak is the preferred method. (An acceptable valve second (or third) gravimetrically determined standard
configuration for the pre-cut method is illustrated in Fig. (either purity or blend) may then be run, using the
3.) The valve position is switched when normal hexane originally obtained response factors, which contain a
and lighter components have traveled through Column 2 concentration of individual components exceeding the
and are in Column 1. At this point, heptanes and heavier expected amounts in the unknowns. If both (or all three)
components are retained in Column 2. When the valve is runs match their respective standards within the precision
reversed, the heptanes plus fraction will elute from Guidelines allowed in Section 8, then the instrument may
Column 2 first. Baseline must be clearly and distinctly be considered linear within that range.
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established before elution of the C7 + peak so an accurate
measurement of this peak can be obtained. After the NOTE 7 – This method omits the need of a gas
elution of n-hexane the run should be terminated and the sample valve on the chromatographic instrument.
valve returned to the initial position. However, several accurate primary NGL standards are
required and the exact point at which nonlinearity occurs
4.3.2 An alternative to the precut method is, after the is not determined.
elution of n-hexane, the carrier gas flow is reversed by
means of a backflush valve operated manually or An alternative and more exacting method is to prepare
automatically. (An acceptable backflush valve response curves from pure components. The procedure for
configuration is shown in Fig. 4.) Reversing carrier flow developing the data necessary to construct these response
causes severe bias, deviations (See Fig. 2). When using curves for all components nitrogen through n-pentane is
electronic digital integrators, exercise care to ensure set forth in GPA Publication 2261, Section 5.
integration does not occur until baseline is adequately re-
established. The resulting irregular shaped C7 + peak is 5.2 For routine analysis using this procedure it is
eluted over a period of time equivalent to time on forward intended that calibration be accomplished by use of a
Figure 4 Backflush Valve Configuration.
4
selected reference standard containing known amounts of where
all components of interest. It is recommended that the
reference standard composition be similar to the one K = response factor
shown in Table III, or closely resemble the composition of
expected unknowns. This approach is valid for all
components that lie within the proven linear range for a X = percent concentration of component
specific gas chromatograph. in reference standard.
NOTE 8 – It is mandatory that the reference P = peak areas in arbitrary unit.

standard be checked for validity when received and
periodically, thereafter. Refer to GPA Technical Standard
2198, most recent revision. 7.1.3 An alternate method of determining response
factors is the use of a single reference component in the
5.3 Using the selected liquid reference standard, standard.
obtain a chromatogram as outlined in Section 4.
7.1.4 Calculate a relative response factor for each
5.3.1. Determine peak areas from the chromatogram, component in accordance with the following relationship
for all components. These data shall be used to calculate (See Table III):
response factors in accordance with Section 7.1.,
CALCULATIONS.
Xi × Pgp
KFi =
5.3.2 If repeatability has not been established, make Pi × Xgp
a second calibration run to determine that the instrument where
will meet the performance criteria established in Section
8. Further information on calibration and calibration KFi = relative response factor for
frequency can be found in GPA Technical Standard 2198,
most recent revision. component i.
Xi = percent concentration of
component i in the reference standard.
6. UNKNOWN SAMPLE RUN
6.1 Obtain a chromatogram of the unknown sample Pi = peak area in arbitrary units for
according to instructions outlined in Section 4. component i.
6.2 Determine peak areas from the chromatogram, for Pgp = peak area of the component
all components. These data shall be used to calculate selected as the reference peak.
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composition of the unknown in accordance with
instructions outlined in Section 7.2, CALCULATIONS. Xgp = percent concentration of the
component in reference standard as the
reference peak.
7. CALCULATIONS From the equation defining the relative
response factor, the component chosen
7.1 Calculation of response factors using a known as the reference peak always has a
reference standard. response factor of 1.000.
7.1.1. Determine the peak area of each component
nitrogen/air through heptanes plus (if applicable) from the
chromatogram of the known reference standard. 7.2 Calculation of volume percent of components in
unknown sample.
NOTE 9 – The heptanes plus peak is considered to
be a single component for the purpose of this calculation. 7.2.1. Determine peak-area of each component
nitrogen/air through heptanes plus (C7+) from the
7.1.2. Calculate a response factor for each of the chromatogram of the unknown sample using the same
above components in accordance with the following arbitrary units as in 7. 1.
relationship. (See Table II):
7.2.2. Calculation of the percent concentration of
each of these components in accordance with the
following relationship (See Table IV):
X
K=
P
5
X=PxK 8. PRECISION
where Repeatability is the expected precision within a

X = percent concentration of component laboratory using the same equipment and same analyst.
in unknown. The repeatability criterion for any component in the liquid
mixture is expressed by the following equation:
P = peak area of each component in
unknown sample.
Repeatability of Component i = 0.08X i2/ 7
K = response factor as determined in 7.1 where Xi = concentration of component i
Totalize percent concentration values

and normalize to 100%. Reproducibility is the expected precision when the
same method is used by different laboratories using
7.2.3 Using the relative response factors calculate the different equipment and different analysis. The
percent concentration of each of these components in reproducibility criterion of any component in the liquid
accordance with the following relationship (See Table V): mixture is expressed by the following equation:
 KFi × Pi  Reproducibility of Component i = 0.1233X1/3

Xi =  n  ×100 i
 ∑ KFi × Pi  where Xi = concentration of component i.

 i=1 
where Table VI provides an example calculation of the

Xi = percent concentration of repeatability and reproducibility requirements for a
component i in unknown. standard.
KFi = relative response factor for

component i. NOTE 11 – The last two numbers in a GPA Standard
refer to the latest revision of that Standard. Contracts
Pi = peak area of component i in usually refer to the latest revision of a standard. Verify
unknown. that you are using the proper version.
∑
n
i=1
(KFi × Pi) = summation of all
9. EXAMPLES
relative response areas in the
chromatogram.
The examples presented in the following tables are
designed to illustrate that the calculations in Section 7 and
Totalize mole percent values and Section 8 may be performed in Mole, Weight, or Liquid
normalize to 100%. Volume Percent.
NOTE 10 – The calculations in Section 7 may be

performed in Mole Percent, Weight Percent or Liquid
Percent.
6
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Table II
Examples of Response Factors Determined from a Reference Standard
Mole % Weight % Liquid Volume %
Peak
Licensee=University of Alberta/5966844001, User=trert, rtyrtyrty

Area Ref. Mole% Mole% Response Factors Wt% Wt% Response Factors LV% LV% Response Factors
Component Std. Run Ref. Std. (x10,000) Ref. Std. (x10,000) Ref. Std. (x10,000)
Nitrogen/Air 311 0.10 0.10 / 311 = 3.2154 0.07 0.07 / 311 = 2.2508 0.04 0.04 / 311 = 1.2862
Not for Resale, 03/04/2015 09:55:59 MST

Methane 3552 1.00 1.00 / 3552 = 2.8153 0.39 0.39 / 3552 = 1.0980 0.60 0.60 / 3552 = 1.6892
Carbon Dioxide 1568 0.50 0.50 / 1568 = 3.1888 0.54 0.54 / 1568=3.4439 0.31 0.31 / 1568 = 1.9770
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Ethane 182108 51.38 51.38 / 182108 = 2.8214 37.63 37.63 / 182108 = 2.0664 48.89 48.89 / 182108 = 2.6847
7
Propane 122825 27.00 27.00 / 122825 = 2.1982 29.00 29.00 / 122825 = 2.3611 26.45 26.45 / 122825 = 2.1535
Iso-Butane 15306 4.00 4.00 / 15306 = 2.6134 5.66 5.66 / 15306 = 3.6979 4.65 4.65 / 15306 = 3.0380
N-Butane 30834 7.00 7.00 / 30834 = 2.2702 8.21 8.21 / 30834 = 2.6626 6.50 6.50 / 30834 = 2.1081
Iso-Pentane 5856 1.00 1.00 / 5856 = 1.7077 1.76 1.76 / 5856 = 3.0055 1.30 1.30 / 5856 = 2.2199
N-Pentane 12280 2.00 2.00 / 12280 = 1.6287 3.52 3.52 / 12280 = 2.8664 2.58 2.58 / 12280 = 2.1010
2,2-Dimethylbutane 132 0.02 0.02 / 132 = 1.5152 0.04 0.04 / 132 = 3.0303 0.03 0.03 / 132 = 2.2727
No reproduction or networking permitted without license from IHS

2,3-Dimethylbutane /
4513 0.90 0.90 / 4513 = 1.9942 1.89 1.89 / 4513 = 4.1879 1.33 1.33 / 4513 = 2.9470
2-Methylpentane
3-Methylpentane /
2401 0.60 0.60 / 2401 = 2.4990 1.26 1.26 / 2401 = 5.2478 0.87 0.87 / 2401 = 3.6235
Cyclopentane
Provided by IHS under license with GPA

N-Hexane 5064 1.00 1.00 / 5064 = 1.9747 2.10 2.10 / 5064 = 4.1469 1.46 1.46 / 5064 = 2.8831

Heptanes Plus 14851 3.50 3.30 / 14851 = 23567 7.93 7.93 / 14851 = 5.3397 4.99 4.99 / 14851 = 3.3600
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Table III
Examples of Relative Response Factors Determined from a Reference Standard Using Ethane as the Reference Peak

Peak
Area Ref. Mole% Mole% Relative Response Wt% Wt% Relative Response LV% LV% Relative Response
Component Std. Run Ref. Std. Factor Ref. Std. Factor Ref. Std. Factor
0.01× 182108 0.07 ×182108 0.04 ×182108
Nitrogen/Air 311 0.10 = 1.1397 0.07 = 1.0893 0.04 = 0.4791

311× 51.38 311× 37.63 311× 48.89
1.00 × 182108 0.39 ×182108 0.60 ×182108
Methane 3552 1.00 = 0.9978 0.39 = 0.5314 0.60 = 0.6292
3552 × 51.38 3552 × 37.63 3552 × 48.89
0.50 × 182108 0.54 ×182108 0.31×182108
Carbon Dioxide 1568 0.50 = 1.1302 0.54 = 1.6666 0.31 = 0.7364
1568 × 51.38 1568 × 37.63 1568 × 48.89
51.38 × 182108 37.63 × 182108 48.89 ×182108
Ethane 182108 51.38 = 1.0000 37.63 = 1.0000 48.89 = 1.0000
182108 × 51.38 182108 × 37.63 182108 × 48.89
8
27.00 ×182108 29.00 ×182108 26.45 ×182108
Propane 122825 27.00 = 0.7791 29.00 = 1.1426 26.45 = 0.8021
122825 × 51.38 122825 × 37.63 122825 × 48.89
4.00 × 182108 5.66 × 182108 4.65 ×182108
Iso-Butane 15306 4.00 = 0.9263 5.66 = 1.7896 4.65 = 1.1316
15306 × 51.38 15306 × 37.63 15306 × 48.89
7.00 × 182108 8.21× 182108 6.50 × 182108
N-Butane 30834 7.00 = 0.8046 8.21 = 1.2886 6.50 = 0.7852
30834 × 51.38 30834 × 37.63 30834 × 48.89
1.00 × 182108 1.76 × 182108 1.30 × 182108
Iso-Pentane 5856 1.00 = 0.6052 1.76 = 1.4545 1.30 = 0.8269
5856 × 51.38 5856 × 37.63 5856 × 48.89
2.00 × 182108 3.52 × 182108 2.58 ×182108
N-Pentane 12280 2.00 = 0.5773 3.52 = 1.3872 2.58 = 0.7826
12280 × 51.38 12280 × 37.63 12280 × 48.89
0.02 × 182108 0.04 ×182108 0.03 ×182108
2,2-Dimethylbutane 132 0.02 = 0.5370 0.04 = 1.4665 0.03 = 0.8466
132 × 51.38 132 × 37.63 132 × 48.89

2,3-Dimethylbutane / 0.90 × 182108 1.89 ×182108 1.33 × 182108
4513 0.90 = 0.7068 1.89 = 2.0267 1.33 = 1.0977
2-Methylpentane 4513 × 51.38 4513 × 37.63 4513 × 48.89
3-Methylpentane / 0.60 × 182108 1.26 × 182108 0.87 ×182108
2401 0.60 = 0.8857 1.26 = 2.5396 0.87 = 1.3497
Cyclopentane 2401× 51.38 2401× 37.63 2401× 48.89
1.00 × 182108 2.10 ×182108 1.46 × 182108

= 0.6999 = 2.0069 = 1.0739

N-Hexane 5064 1.00 2.10 1.46
5064 × 51.38 5064 × 37.63 5064 × 48.89
3.50 × 182108 7.93 × 182108 4.99 ×182108
Heptanes Plus 14851 3.50 = 0.8353 7.93 = 2.5841 4.99 = 1.2516
14851× 51.38 14851× 37.63 14851× 48.89
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Table IV

Calculation of Unknown Sample Using Response Factors from Table II
Peak Mole% Response Wt% Response LV% Response
Area Ref. Factors Un-normalized Normalized Factors Un-normalized Normalized Factors Un-normaized Normalized

Component Std. Run (x10,000) Mole % Mole % (x10,000) Wt % Weight % (x10,000) LV% LV%
Nitrogen/Air 30 3.2154 0.01 0.01 2.2508 0.01 0.01 1.2862 0.00 0.00
Methane 5649 2.8153 1.59 1.65 1.0980 0.62 0.55 1.6892 0.95 0.95
Carbon Dioxide 2112 3.1888 0.67 0.70 3.4439 0.73 0.64 1.9770 0.42 0.42
Ethane 85298 2.8214 24.07 24.97 2.0664 17.63 15.61 2.6847 22.90 22.80
9
Propane 153852 2.1982 33.82 35.09 2.3611 36.33 32.17 2.1535 33.13 32.98
Iso-Butane 37359 2.6134 9.76 10.13 3.6979 13.81 12.23 3.0380 11.35 11.30
N-Butane 43219 2.2702 9.81 10.18 2.6626 11.51 10.19 2.1081 9.11 9.07
Iso-Pentane 28445 1.7077 4.86 5.04 3.0055 8.55 7.57 2.2199 6.31 6.29
N-Pentane 29647 1.6287 4.83 5.01 2.8664 8.50 7.53 2.1010 6.23 6.20
2,2-Dimethylbutane 191 1.5152 0.03 0.03 3.0303 0.06 0.05 2.2727 0.04 0.04
5558 1.9942 1.11 1.15 4.1879 2.33 2.06 2.9470 1.64 1.63

2-Methylpentane
3-Methylpentane /
2970 2.499 0.74 0.77 5.2478 1.56 1.38 3.6235 1.08 1.07
Cyclopentane
N-Hexane 6247 1.9747 1.23 1.28 4.1469 2.59 2.29 2.8831 1.80 1.79

Heptanes Plus 16318 2.3567 3.85 3.99 5.3397 8.71 7.72 3.3600 5.48 5.46
Total 96.38 100.00 112.92 100.00 100.45 100.00
Table V

Calculation of Unknown Sample Using Relative Response Factors from Table III
Peak Normalized Normalized Normalized
Area Ref. Mole% Relative Mole % Wt% Relative Wt % LV% Relative LV %
Pi × KFi Pi × KFi Pi × KFi

Std. Run Response Factors ×100 Response Factors ×100 Response Factors ×100
Component (P) (KFi) P X KFi ∑ P × KF
i (KFi) P X KFi ∑ P × KF
i (KFi) P X KFi ∑ P × KF
i
Nitrogen/Air 30 1.13970 34 0.01 2.2508 0.01 0.01 1.2862 0.00 0.00
Methane 5649 0.99780 5637 1.65 1.0980 0.62 0.55 1.6892 0.95 0.95
Carbon Dioxide 2112 1.13020 2387 0.70 3.4439 0.73 0.64 1.9770 0.42 0.42
10
Ethane 85298 1.00000 85298 24.97 2.0664 17.63 15.61 2.6847 22.90 22.80
Propane 153852 0.77910 119866 35.09 2.3611 36.33 32.17 2.1535 33.13 32.98
Iso-Butane 37359 0.92630 34606 10.13 3.6979 13.81 12.23 3.0380 11.35 11.30
N-Butane 43219 0.80460 34774 10.18 2.6626 11.51 10.19 2.1081 9.11 9.07
Iso-Pentane 28445 0.60520 17215 5.04 3.0055 8.55 7.57 2.2199 6.31 6.29
N-Pentane 29647 0.57730 17115 5.01 2.8664 8.50 7.53 2.1010 6.23 6.20
2,2-Dimethylbutane 191 0.53700 103 0.03 3.0303 0.06 0.05 2.2727 0.04 0.04

5558 0.70680 3928 1.15 4.1879 2.33 2.06 2.9470 1.64 1.63
2-Methylpentane
3-Methylpentane /
2970 0.88570 2631 0.77 5.2478 1.56 1.38 3.6235 1.08 1.07
Cyclopentane
N-Hexane 6247 0.69990 4372 1.28 4.1469 2.59 2.29 2.8831 1.80 1.79

Heptanes Plus 16318 0.83530 13630 3.99 5.3397 8.71 7.72 3.3600 5.48 5.46
--`,```,,,```,,,,``,`,,,,``,```-`-`,,`,,`,`,,`---
Total 341596 100.00 112.92 100.00 100.45 100.00
Table VI
Example of Repeatability and Reproducibility Criteria for a Reference Standard
--`,```,,,```,,,,``,`,,,,``,```-`-`,,`,,`,`,,`---
Concentration Repeatability Reproducibility Concentration Repeatability Reproducibility Concentration Repeatability Reproducibility

Component in Ref. Std. (+/- Mole %) (+/- Mole %) in Ref. Std. (+/- Wt %) (+/- Wt %) in Ref. Std. (+/- LV %) (+/- LV %)
Nitrogen/Air 0.10 0.04 0.06 0.07 0.04 0.05 0.04 0.03 0.04
Methane 1.00 0.08 0.12 0.39 0.06 0.09 0.60 0.07 0.10
Carbon Dioxide 0.50 0.07 0.10 0.54 0.07 0.10 0.31 0.06 0.08
11
Ethane 51.38 0.25 0.46 37.63 0.23 0.41 48.89 0.24 0.45
Propane 27.00 0.21 0.37 29.00 0.21 0.38 26.45 0.20 0.37
Iso-Butane 4.00 0.12 0.20 5.66 0.13 0.22 4.65 0.12 0.21
N-Butane 7.00 0.14 0.24 8.21 0.15 0.25 6.50 0.14 0.23
Iso-Pentane 1.00 0.08 0.12 1.76 0.09 0.15 1.30 0.09 0.13
N-Pentane 2.00 0.10 0.16 3.52 0.11 0.19 2.58 0.10 0.17
2,2-
0.02 0.03 0.03 0.04 0.03 0.04 0.03 0.03 0.04
Dimethylbutane

2,3-
0.90 0.08 0.12 1.89 0.10 0.15 1.33 0.09 0.14
Dimethylbutane /
3-Methylpentane
0.60 0.07 0.10 1.26 0.09 0.13 0.87 0.08 0.12
/ Cyclopentane

N-Hexane 1.00 0.08 0.12 2.10 0.10 0.16 1.46 0.09 0.14
Heptanes Plus 3.50 0.11 0.19 7.93 0.14 0.25 4.99 0.13 0.21
Appendix A
Fidelity of Selected Reference Standard
The reader is referred to GPA 2198 (most recent revision) The procedures outlined in GPA 2198 should be used to
for details of the "Fidelity of Selected Reference Blends", monitor both instrument performance and reference blend
as well as several additional quality control procedures. fidelity.
--`,```,,,```,,,,``,`,,,,``,```-`-`,,`,,`,`,,`---
12
Appendix B
Calculation Performed in Association with Liquid Analysis
PREFACE Constant values for hexanes plus (C6+) or heptanes plus
All physical constants used in these calculations should (C7+) if not actually determined by extended analysis
come from the most recent edition of GPA 2145. The should be mutually agreed upon by all concerned parties.
constants used in the examples that follow are from GPA
2145-09. For ease of hand calculations in the examples shown the
number of significant figures does not match those shown
The following physical constants not listed in GPA 2145 in GPA-2145. Precision of numbers in computer
have been used in some of the calculations: generated calculations should match that of GPA-2145.
Rounding of numbers can cause some differences in final
0.25636 = vapor pressure of H2O (psia) @60°F results. Computer generated calculations should only
(reference: U.S. Bureau of Standards) round those final numbers displayed on analyses, not
numbers generated in intermediate calculations.
1230 = vapor pressure of CO2 (psia) @ 100°F
For those calculations that are pressure dependent, the
5000 = vapor pressure of N2 (psia) @ 100°F mathematics should be carried out using the constants at a
pressure base of 14.696 and the final result converted to
R = Gas Constant = 1545.3504 ft. – lbf/lb – mole °R the desired pressure base after all other mathematical
functions are completed. Conversion of the physical
Cu.ft./lb -mole of any gas at 14.696 psia and 60°F constants to equivalent values at other pressure bases or
the use of generated secondary factors prior to performing
V (R × T) calculations is not recommended.
= =
n P It is further recommended that computer software be
written to follow these methods and recommendations and
1545.3504 × (459.67 + 60) that hardbound documentation of the software programs
=
144 × 14.696 be maintained and available at all times.
= 3.79.48357 B.1 Calculation of Weight Fraction, Mole Fraction,

Molecular Weight, and Relative Density of Liquefied
Product from Liquid Volume Analysis.
Column 1 Column 2 Column 3 Column 4 Column 5 Column 6 Column 7 Column 8 Column 9 Column 10
Sample Absolute Weight Sample Wt. Mol Sample Sample Mol Sample Relative Sample
LV Fraction Density Lbs. Fraction Weights Mols Fraction Mol Weight Density Density
by
component
Components
GPA-2145 Col.1xCol.2 Col.3/Col.3 GPA-2145 Col.3x100 / Col.6/Col.6 Col.7xCol.5 GPA-2145 Col.1xCol.9
Tot Col.5 Tot
Nitrogen 0.0001 6.7271 0.0007 0.0002 28.0134 0.0024 0.0003 0.0074 0.80687 0.00008
Methane 0.0165 2.5000 0.0413 0.0098 16.0425 0.2571 0.0285 0.4565 0.30000 0.00495
Carbon
Dioxide 0.0070 6.8129 0.0477 0.0113 44.0095 0.1084 0.0120 0.5278 0.81716 0.00572
Ethane 0.2497 2.9704 0.7417 0.1758 30.0690 2.4667 0.2730 8.2083 0.35628 0.08896
Propane 0.3509 4.2285 1.4838 0.3517 44.0956 3.3649 0.3724 16.4207 0.50719 0.17797
Iso-Butane 0.1013 4.6925 0.4754 0.1127 58.1222 0.8178 0.0905 5.2606 0.56283 0.05701
N-Butane 0.1018 4.8706 0.4958 0.1175 58.1222 0.8531 0.0944 5.4872 0.58420 0.05947
Iso-Pentane 0.0504 5.2120 0.2627 0.0623 72.1488 0.3641 0.0403 2.9071 0.62514 0.03151
N-Pentane 0.0501 5.2584 0.2634 0.0624 72.1488 0.3651 0.0404 2.9155 0.63071 0.03160
Hexanes Plus
* 0.0722 5.6325 0.4067 0.0964 93.1890 0.4364 0.0483 4.5005 0.67559 0.04878
Totals: 1.0000 4.2191 1.0000 9.0360 1.0000

Molecular Weight: 46.6916
Relative
Density: 0.50606
* Arbitrarily assumed value (used is average value not determined)
13 --`,```,,,```,,,,``,`,,,,``,```-`-`,,`,,`,`,,`---

B.2. Calculation of API Gravity of Liquefied Product. Note: Vapor Pressure (psig) = Vapor Pressure (psia) -14.7
Liquid Density (lb/gal) = Relative Density x lb/gal of H2O = 460.8 - 14.7
= 0.5062 x 8.3372 = 446.1
= 4.2203 B.7 Calculation of BTU per Cubic Foot, BTU per Gallon
of Liquefied Product – See GPA-2172
B.3 Calculation of API Gravity of Liquefied Product.
B.8 Calculation of BTU per Pound of Liquefied Product –
API Gravity = (141.5 / Relative Density) – 131.5 See GPA-2172
= (141.5 / 0.5062) – 131.5 B.9 Calculation of 26-70 Gasoline Content of Liquefied

Product.
= 148.0
Column 1 Column 2 Column 3
B.4 Calculation of Cubic Foot of Vapor / Gallon of Sample Vapor Partial
Liquefied Product. Mol Fraction Pressure Pressure
Components psig
GPA-2145 Col.1xCol.2
lb / gal × 379.48357 14.696
cu. ft./gal @ PB = × Iso-Pentane 0.0402 20.474 0.8231
mol. wt. PB N-Pentane 0.0404 15.576 0.6293
Hexanes Plus * 0.0483 3.517 0.1699
Where: PB = Desired Pressure Base
A= 0.1289 B= 1.6222
--`,```,,,```,,,,``,`,,,,``,```-`-`,,`,,`,`,,`---
379.48357 = cu. ft. volume occupied by one lb.
Mol. of any gas @ 14.696 psia and 60°F.
Example: cu. ft./gal @ 14.730 psia = * Arbitrarily assumed value (used is average value not determined)
4.2203×379.48357 14.696 Mole Fraction of NC4 Required to Product 26 psi
× Gasoline:
46.687 14.730
= 34.2245 [(27.5× A) - B] = mole fraction of NC required
4
24.067
B.5 Calculation of Relative Density of Vapor of Liquefied
Product – See GPA-2172
[(27.5×0.1283) -1.6222] = 0.0792
B.6 Calculation of Vapor Pressure 24.067
Column 1 Column 2 Column 3 Where: 27.5 = True Vapor Pressure (psia) required to
Sample Vapor Component obtain an ASTM Reid Vapor Pressure of 26 psi
Mol Fraction Pressure Vapor
Components psia Pressure 24.067 = MC4 Vapor Pressure (51.567) – required
GPA-2145 Col.1xCol.2 pressure (27.5)
Nitrogen 0.0003 5000.000 1.5
Methane 0.0285 5000.000 142.5 A = Sum of Mole Fraction of C5+ Components
Carbon Dioxide 0.0121 1230.000 14.9
Ethane 0.2730 800.000 218.4 B = Sum of Partial Pressures of C3+ Components
Propane 0.3723 188.620 70.2
Iso-Butane 0.0905 72.644 6.6 Liquid Volume Fraction on NC4 Required to Produce 26
N-Butane 0.0944 51.567 4.9 psi Gasoline:
Iso-Pentane 0.0402 20.474 0.8
N-Pentane 0.0404 15.576 0.6 Liquid Volume Fraction NC4 =
Hexanes Plus * 0.0483 3.520 0.2 Liq. Vol. Fraction NC4 from Analysis
Mol Fraction NC4 Required×
Mol Fraction NC4 from Analysis
Totals: 1.0000 Vapor Pressure = 460.6
Liquid Volume Fraction NC4 = 0.0792×

0.1018
0.0944
* Arbitrarily assumed value (used is average value not
determined) = 0.0854
14
Components Liq, Vol. Fraction Mol Fraction
N-Butane 0.1018 0.0944 For 14 psi Gasoline Calculation:
Iso-Pentane 0.0504 0.0403
If liquid volume fraction of NC4 required is greater than
N-Pentane 0.0501 0.0404
the liquid volume of NC4 present in the product then IC4
Hexanes Plus * 0.0722 0.0483 should be added into the above calculation and 57.394
substituted for 24.067 as the difference between IC4
26 psia Gasoline = 0.2745 0.2234 Vapor Pressure and required Vapor Pressure.
* Arbitrarily assumed value (used is average value not Calculation of Excess Butane Liquid Volume
determined)
Excess NC4 = NC4 Liq. Vol. Fraction from analysis –
NOTE – IC5, NC5, and NC6 from calculation B.6 based Liq. Vol. Fraction IC4 required
upon liquid sample mole fraction.
= 0.1018 – 0.0854
NOTE – Calculation of 14 psi Gasoline of Liquefied
= 0.0164
Product:
NOTE – If excess NC4 is a negative number the IC4 is
14 psi Gasoline content is calculated in exactly the same
used in the preceding calculations and excess Butane is
manner as 26 psi Gasoline with the following two
calculated as:
changes:
Excess IC4 = IC4 Liquid Volume Fraction from analysis –
(1) 15.25 is used in place of 27.5 as the required Vapor
Liquid Volume Fraction IC4 required –
Pressure to obtain a correct reading of 14 psi.
NOTE – If excess IC4 is a negative number the result is
(2) 36.317 is used in place of 24.067 as the difference the liquid fraction of Butane that would have to be added
between NC4 Vapor Pressure and required pressure. to the liquefied product.
NOTE – For 26 psi Gasoline Calculation:
If liquid volume fraction of NC4 required is greater than

the liquid volume of NC4 present in the product then IC4
should be added into the above calculation and 45.144
substituted for 24.067 as the difference between IC4
Vapor Pressure and required Vapor Pressure.
--`,```,,,```,,,,``,`,,,,``,```-`-`,,`,,`,`,,`---
15

Gpa STD 2177-2013

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GPA Standard 2177-13

Analysis of Natural Gas Liquid Mixtures Containing Nitrogen and

Adopted as Tentative Standard. 1977

Gas Processors Association

Copyright Gas Processors Association

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“Copyright© 2013 by Gas Processors Association. All rights reserved.

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3.1.5 Temperature Control – The chromatographic

Figure 4 Backflush Valve Configuration.

NOTE 8 – It is mandatory that the reference P = peak areas in arbitrary unit.

where Repeatability is the expected precision within a

Totalize percent concentration values

 KFi × Pi  Reproducibility of Component i = 0.1233X1/3

 ∑ KFi × Pi  where Xi = concentration of component i.

where Table VI provides an example calculation of the

KFi = relative response factor for

NOTE 10 – The calculations in Section 7 may be

Copyright Gas Processors Association

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No reproduction or networking permitted without license from IHS

Provided by IHS under license with GPA

Copyright Gas Processors Association

Licensee=University of Alberta/5966844001, User=trert, rtyrtyrty

Not for Resale, 03/04/2015 09:55:59 MST

No reproduction or networking permitted without license from IHS

Provided by IHS under license with GPA

Copyright Gas Processors Association

Licensee=University of Alberta/5966844001, User=trert, rtyrtyrty

Not for Resale, 03/04/2015 09:55:59 MST

No reproduction or networking permitted without license from IHS

Provided by IHS under license with GPA

Licensee=University of Alberta/5966844001, User=trert, rtyrtyrty

Not for Resale, 03/04/2015 09:55:59 MST

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Not for Resale, 03/04/2015 09:55:59 MST

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= 3.79.48357 B.1 Calculation of Weight Fraction, Mole Fraction,

Totals: 1.0000 4.2191 1.0000 9.0360 1.0000

* Arbitrarily assumed value (used is average value not determined)

Copyright Gas Processors Association

Liquid Density (lb/gal) = Relative Density x lb/gal of H2O = 460.8 - 14.7

= 0.5062 x 8.3372 = 446.1

= (141.5 / 0.5062) – 131.5 B.9 Calculation of 26-70 Gasoline Content of Liquefied

Liquid Volume Fraction NC4 = 0.0792×

If liquid volume fraction of NC4 required is greater than

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