United States
             Environmental Protection
             Agency
                Office of Mobile Source Air Pollution Control
                Emission Control Technology Division
                2565 Plymouth Road
                Ann Arbor, Michigan 48105
EPA 460/3-83-009
March 1983
             Air
&EPA
Calculation of Emissions and Fuel
Economy When Using Alternate
Fuels

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                                           EPA 460/3-83-009
Calculation of  Emissions  and Fuel  Economy
            When  Using  Alternate  Fuels
                                 by

                            Charles M. Urban

                         Southwest Research Institute
                            6220 Culebra Road
                          San Antonio, Texas 78284

                           Contract No. 68-03-3073
                            Work Assignment 8

                       EPA Project Officer: Robert J. Garbe
                              Prepared for

                     ENVIRONMENTAL PROTECTION AGENCY
                     Office of Mobile Source Air Pollution Control
                       Emission Control Technology Division
                            2565 Plymouth Road
                          Ann Arbor, Michigan 48105
                              March 1983
                             Tf.,1, HrjvirorTentsT Proto
                               ,-.", ^ , J,;.-. ',:r- ;;",-'.
                             .  , '). I'L-.'.XJUI:! l-.:r,:;3t, I.uora 1670
                             Cr.ic^'0, Hi  .60604

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This report is issued by the Environmental Protection Agency to report
technical data of interest to a limited number of readers.  Copies are
available free of charge to Federal employees, current contractors and
grantees, and nonprofit organizations - in limited quantities - from
the Library Services Offices, Environmental Protection Agency,
2565 Plymouth Road, Ann Arbor, Michigan, 48105.
This report was furnished to the Environmental Protection Agency by
Southwest Research Institute, 6220 Culebra Road, San Antonio, Texas,
in fullfillment of Work Assignment 8 of Contract No. 68-03-3073.  The
contents of this report are reproduced herein as received from South-
west Research Institute.  The opinions, findings, and conclusions
expressed are those of the author and not necessarily those of the
Environmental Protection Agency.  Mention of company or product names
is not to be considered as an endorsement by the Environmental Ptotec-
tion Agency.
                        Publication No. 460/3-83-009
                                     11

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                                  FOREWORD
     This Work Assignment was initiated by the Control Technology Assessment
and Characterization Branch, Environmental Protection Agency, 2565 Plymouth
Road, Ann Arbor, Michigan 48105.  The effort on which this report is based
was accomplished by the Department of Emissions Research of Southwest
Research Institute, 6220 Culebra Road, San Antonio, Texas 78284.  This
program, authorized by Work Assignment 8 under Contract 68-03-3073, was
initiated May 26, 1982 and was completed September 28, 1982.  The program
was identified within Southwest Research Institute as Project 05-6619-008.

     This Work Assignment was conducted by Mr. Charles Urban, Project Leader.
Mr. Charles Hare was Project Manager and was involved in the initial technical
and fiscal negotiations and subsequent major program decisions.  The EPA
Project Officer was Mr. Robert J. Garbe of the Technical Support Staff,
Environmental Protection Agency.
                                    111

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                                  ABSTRACT
     This report provides methods for the calculation of vehicle emissions
and fuel consumption when nonstandard fuels are used.  Methods of analysis,
required for evaluation of alternate fuels, are included by reference or as
Appendices to this report.
                                     IV

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                             TABLE OF CONTENTS

                                                                   Page

FOREWORD                                                            iii

ABSTRACT                                                             iv

LIST OF ANALYTICAL METHODS AND CALCULATIONS                          vi

I.   INTRODUCTION                                                     1

II.  EQUIPMENT, INSTRUMENTATION AND ANALYTICAL METHODS                3

     A.  CVS Dilution Requirements                                    3
     B.  Emissions Instrumentation                                    4
     C.  Analytical Methods                                           4

III. FUEL COMPOSITION                                                 7

     A.  Blends of Known Composition                                  7
     B.  Fuels of Unknown Composition                                 7

IV.  EXHAUST EMISSIONS                                               11

     A.  Exhaust Organic Matter Composition                          11
     B.  Calculation of Gaseous Exhaust Emissions                    12
     C.  Calculation of Particulate Exhaust Emissions                20
     D.  Non-Methane Hydrocarbons                                    20
     E.  Unregulated Exhaust Emissions                               20

V.   FUEL ECONOMY                                                    21

     A.  Calculation of Fuel Economy                                 21
     B.  Fuel Economy Related Considerations                         23

VI.  EVAPORATIVE EMISSIONS                                           25

     A.  Evaporative HC Composition for Hydrocarbon Fuels            25
     B.  Evaporative Organic Matter Composition for Other Fuels      26
     C.  Calculation of Evaporative Emissions                        26

REFERENCES                                                           27

SELECTED BIBLIOGRAPHY                                                28

APPENDICES

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                LIST OF ANALYTICAL METHODS AND CALCULATIONS




                                                                   Page




CVS Dilution Requirements                                             3




CO2 Emissions Concentrations                                          4




List of Analytical Methods                                            5




Component Fractions in Fuel Blends                                    8




Allowable Accuracies for Fuel Elemental Analysis                      9




Calculation of Gaseous Exhaust Emissions                             12




Example Emission Calculation for Methanol Fuel                       18




Calculation of Particulate Exhaust Emissions                         20




List of Possible Unregulated Emissions                               20




Calculation of Fuel Economy                                          21




Example Fuel Economy Calculation for Methanol Fuel                   23




Calculation of Energy Based Fuel Consumption                         23




Calculation of Evaporative Emissions                                 26
                                    VI

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                              I.  INTRODUCTION
     The objective of this Work Assignment was to compile and document pro-
cedures to follow when calculating and reporting exhaust or evaporative
emissions data and carbon balance fuel economy data from vehicles operating
on hydrogen and carbon containing fuels other than commercial gasoline and
Diesel fuel.

     This report describes calculational procedures for use in light-duty
applications when using alternate fuels.  In addition to the calculational
changes that are required to the light-duty certification procedure, some
equipment and instrumentation changes may also be required.  Discussion of
these equipment and instrumentation requirements is also included in this
report.

     The composition of the evaporative and the exhaust organic matter with
alternate fuels generally differs from the composition of the hydrocarbons
used to establish the HC emissions standard.  The relationship between the
organic matter value for an alternate fuel and the HC emissions value for a
standard gasoline or diesel fuel have not been established.  Therefore, no
procedure is included for the calculation of a single composite value for
organic matter when alternate fuels are used.

     The format used for mathematical equations in this report is in accor-
dance with that used in the Code of Federal Regulation.* '    Computations
are to be performed in accordance with the IBM hierarchy of operations.

     Although specific application to the heavy-duty transient procedure
is not included, the procedures given are generally applicable.  The methods
given can be fairly readily adapted for use with the heavy-duty transient
procedure.
*Numbers in parentheses designate references at the end of this report.

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           II.  EQUIPMENT, INSTRUMENTATION AND ANALYTICAL METHODS


     Fuels having higher hydrogen-to-carbon ratios produce more water and
less CO2 for equal energy output.  Therefore, a higher than normal CVS di-
lution flow rate could be required to keep water condensation from occurring.
A higher CVS flow rate (CO2 emissions would also be directly affected by
lower CO2 production) could result in emissions concentrations that are
lower than the prescribed accuracies of the normally used emissions instru-
ments.  Therefore, the CVS flow rate and the exhaust emissions instrumen-
tation are essential considerations when alternate fuels are to be evaluated.

A.   CVS Dilution Requirements

     The CVS flow capacity of 300 to 350 scfm that is designated in the
light-duty certification procedure as being adequate, is based on currently
formulated gasoline and Diesel fuels. '*)  Fuels containing a higher hydrogen-
to-carbon ratio produce more water and can require a higher CVS dilution flow
rate to keep condensation of water from occurring in the sample bags.  Since
the currently specified CVS flow rate generally prevents water condensation
from occurring, when using gasoline or Diesel fuel, the CVS flow rate for an
alternate fuel that is sufficient for most light-duty vehicles can be esti-
mated as follows:

            ACVSFR = (AFFH/ALHV)X5><107

             Where:
                 ACVSFR = CVS flow rate for alternate fuel that is
                          sufficient for most vehicles, cfm
                 AFFH   = Fuel fraction hydrogen of the alternate fuel
                 ALHV   = Lower heating value of the alternate fuel, Btu/lg

     The resulting flow rate (ACVSFR),  however, is often much higher than is
actually required, especially for smaller, fuel efficient vehicles.  Therefore,
the determination of the actual required CVS flow rate is given as follows:

            RCVSFR = 16.6XAMPHXFDENXFFH/(MPGX(SSH - TSH))

             Where:
                 RCVSFR = Required CVS flow rate, scfm
                 AMPH   = Average speed, mph (16 minimum for the
                          cycles of the FTP)
                 FDEN   = Density  of the fuel, g/m&
                 FFH    = Fuel fraction hydrogen, mass/mass
                 MPG    = Fuel economy, mpg
                 SSH    = Specific humidity of saturated air at
                          minimum sample bag temperature, Ib/lb
                 TSH    = Actual specific humidity of the dilution air
                          at test conditions, Ib/lb

             Note:  Derivation of RCVSRF is given in Appendix A-l.
                                      3

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     Combining the provisions in the ACVCFR and the RCVSFR equations, and
making several assumptions to enable simplification, results in the following
equation for estimation of the required CVS flow rate for the FTP:

          ECVSFR = 45,OOQXFDENXFFH/MPG

When the fuel economy for the vehicle is not known, it can be estimated
using the fuel economy for a similar vehicle operating on certification
fuel multiplied by the ratio of the lower heating values per unit volume:

          AMPG - CMPGXCLHV/ALHV

          Where:
              AMPG = Fuel economy with the alternate fuel, mpg
              CMPG = Fuel economy with certification fuel, mpg
              CLHV = Lower heating value of certification fuel (18,300 Btu/lb)
              ALHV = Lower heating value of the alternate fuel

B.   Emissions Instrumentation

     When fuels with high hydrogen-to-carbon ratios are used, emissions
instrumentation having lower ranges may be required.  Unless the emission
rates are known, however, the necessary instrument ranges can not be pre-
determined.  Therefore, the recommendation is that applicability of ranges
be determined from actual measuremnt of emissions at the onset of testing.

     CC>2 emission concentrations, however, can be estimated using the CVS
flowrate, the carbon fraction of the fuel, and the fuel consumption on a
weight basis.  The equation, derived in Appendix A-2, is as follows:

          CO2% =  (451XAMPHXFDEN)/(FEXCVSFR)

          Where:
              CO2%  = CO2 concentration in the Dilute Exhaust Sample, Percent
              AMPH  = Average Speed of the Cycle, mph
              FDEN  = Fuel Density, g/m
              FE    = Cycle Fuel Economy, mpg
              CVSFR = Flowrate of the CVS, scfm

C.   Analytical Methods

     In  several of the calculations required for alternate fuels, additional
analyses of  the fuel or the emissions are specified or recommended.  Some
analytical methods are listed on the following page.

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                    Method                              Source
Determination of FID Response Factor                Appendix A-3


Measurement of Aldehydes and Ketones                Appendix A-4


Measurement of Individual Hydrocarbons              Reference 3

                                                              (4\
Methane Measurement Using Gas Chromatograph         SAE J1151av '




     Additional methods for special applications are listed as follows:




                Method                                  Source
Measurement of Methanol                             Appendix A-5


Measurement of Ethanol                              Appendix A-6


Measurement of Tertiary Butyl Alcohol               Reference 6

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                           III.  FUEL COMPOSITION
     In the procedure for certification of light-duty vehicles, a specified
hydrogen-to-carbon ratio and density are assumed to be applicable for all
petroleum based fuels meeting the prescribed specifications.  When using
alternate fuels, however, the differences in fuel composition and density
are sufficiently large to make it essential that the actual values be
determined and used.

     The calculations of emissions and fuel economy, for alternate fuels,
require the use of the weight ratios of carbon, hydrogen, oxygen, and the
sum of the other elements in the fuel.  For the calculation of fuel economy,
the density of the fuel is also required.

     For blends of known composition, the weight ratios of the constituents
can either be measured or calculated.  For fuels of unknown composition,
however, determination of the elemental composition is essential.  Due to
the uncertainties involved when various liquids are blended together, it
is recommended that fuel density always be determined by actual measurement
(unless the effects of blending on density are specifically known for the
specific blended fuel).

     For gaseous fuels/ such as propane, a significant quantity of impurities
(e.g., 062) may be present in the fuel which would have an impact on the
emissions and fuel economy calculations.  Therefore, it is also important
to determine the weight ratios of carbon, hydrogen, oxygen, and the sum of
the other elements when gaseous fuels are used.

A.   Blends of Known Composition

     When blending a fuel of known composition, the elemental weight ratios
can be determined by calculation.  The method will be demonstrated using a
blend of a gasoline, meeting the certification fuel specifications, and
methanol (assuming such a blend is achieved).

     For gasoline, a hydrogen-to-carbon ratio  (HCR) of 1.85 to 1 can be
assumed.  This results in fuel carbon and hydrogen fractions of weight
(GFC and GFH) of 0.866 and 0.134, respectively.  Methanol has an MFC and
MFH of 0.375 and 0.126, respectively.  The remaining component in methanol
is oxygen,  with an MFo of 0.499.  The resulting carbon, hydrogen, and oxygen
fractions in a blend of gasoline and methanol are on the following page.

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          BFX = ((Wt% Gas)XGFX + (Wt% Meth) >% Gas) XGDENX100 _
                                   Gas)XGDEN + (Vol.% Meth)XMDEN
              B, G, & M = Blend, Gasoline and Methanol
              X = Carbon, hydrogen or oxygen
              DEN = Density, g/m

          Assume 90% Gasoline and 10% Methanol by Weight:
              BFC = (90XQ.866 + 1QXQ. 375)/100 = 0.817
              BFH = (90XQ.134 + 10XQ.126)/100 = 0.133
              BFO = (90XQ.OOO + 10XQ.499)/100 = 0.050

The elemental fractions in a blended fuel can also be determined by elemental
analyses of the fuel blend.  Methods for such analyses are discussed in the
following Section III.B.  Due to the uncertainties involved in blending fuels,
it is recommended that generally the density of the resultant fuel blend be
determined by actual measurement.

B.   Fuels of Unknown Composition

     For fuels of unknown composition, the elemental fractions can be deter-
mined only by actual analysis.  The carbon, hydrogen and oxygen values, and
occasionally the nitrogen value, are required.  Analysis of liquid fuels for
these elements is extremely difficult, and standard ASTM methods are not
currently available.  It is recommended that such analysis be conducted only
by a laboratory known to have the necessary expertise.

     There does not appear to be general agreement on the best methods of
analysis for these  elements.  The commerically available C, H, N, O and S
analyzers were not specifically designed for, and do not generally appear
to provide, satisfactory analysis of liquid fuels.  Therefore, such analyzers
are not a simple solution to the measurement problem and their use should
be approached with caution.

     Some example methods of elemental analysis for liquid fuels are as
follows:  Carbon and hydrogen have been satisfactorily measured using an
elemental analyzer, or gravimetrically using a modified ASTM D-3178 method.
Nitrogen has been satisfactorily measured using pyrochemiluminescence.
Oxygen has been satifactorily measured using neutron activation analysis.
In all cases, it appears that a very high level of expertise is essential
to obtaining satisfactory analysis of these elements in liquid fuels.

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     For general guidance purposes, the accuracies of the analyses should
be within the following limits:

                      	Analysis Accuracy as;	
           Element         % of Value3            % of Fuela
          Carbon      0.5                   0.3
          Hydrogen    0.5                   0.3
          Oxygen      (0.2/Value  + 0.3)    (0.2 + C.^ .^^ .
          Nitrogen    (0.2/Value  +0.3)    (0.2 + 0.3xvalue )

          Total of All                            1.0
          a
           Use the analysis accuracy having the lowest absolute
           number
           Value as a weight fraction of total fuel

The limits given represent  the extremes; an effort should be made to obtain
better analysis accuracies than these extreme limits given.

     The total of the weight fractions of the C, H, O and N in the fuel may
not add up to a total of 1.000.  Computer inputs include the fuel fraction
of C, H, O and other elements.  If the total for C, H, O and N is less than
1.000, add the difference to the value for other elements. If the total for
C, H, 0 and N is greater than 1.000, subtract the difference from the value
for oxygen (0) or the value for other elements, as appropriate.

     The acceptable level of sulfur is generally sufficiently low so that
the amount of sulfur present does not significantly affect the standard
emissions and fuel consumption calculations.  Amount of sulfur in the fuel,
however, is generally considered to be of sufficient importance to justify
determination of sulfur.  Depending on the type of fuel involved and its
source, it may also be worthwhile to include additional analyses, such as
ash content,  gum, and some additional specific elements.  Standard ASTM
methods are available for sulfur, ash, gum, and several specific elements.

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                           IV.  EXHAUST EMISSIONS
     The basic calculations used in the certification of light-duty vehicles
are applicable for use with alternate fuels.  A number of the parameters
utilized, however, must be changed to account for the potentially large
differences in fuel and exhaust organic matter composition.  In addition,
no generally acceptable method is currently available for determination
of a meaningful composite value for the organic matter when using alternate
fuels.  This section describes the determination of the required parameters
and the calculational methods to enable incorporation of these parameters.

A.   Exhaust Organic Matter Composition

     The composition of the exhaust hydrocarbon emissions affects the
response factor of the FID instrument and the density of the HC emissions.
The current light-duty certification procedure assumes that the overall
FID resposne factor for the hydrocarbons in the exhaust is essentially
equal to the FID response factor for propane.  For alternate fuels with
significantly different composition such response factor assumption is
inappropriate.

     The only method determined to be generally acceptable for alternate
fuels is to measure the individual components of the organic matter in the
exhaust, and then to calculate and report all of the major constituents.
Unfortunately, this method is impractical in many situations. Therefore,
it is recommended that measurement, calculation, and reporting of the
individual components of the exhaust organic matter be done to the extent
practical.  Generally, the summation of the individual components is
inappropriate, and should not be done, when alternate fuels are used.

     In cases where an exact determination is not essential, a simpler
determination can be made by assuming the composition of the organic
matter in the exhaust is equal to that in the fuel.  Determine the FID
response factor for the fuel using the method given in Appendix A-3,
and apply this factor to the FID measured value of the exhaust.  The
method used for determination of organic matter should always be identified
for any such data reported.
                                     11

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B.   Calculation of Gaseous Exhaust Emissions

     The following calculations for exhaust emissions are recommended for
use when non-standard carbon bearing fuels are utilized.  These calculations
are based on the calculations given in 40 CFR Part 86, Subpart B, 86.144-78,
with latest revisions incorporated.  The basic format used in 86.144 has
been retained.  Changes or additions to the calculational methods in
86.144-78 are identified by asterisk(*) and  are  derived in Appendix B-2.

    * Analyses, in addition to those required in the certification procedure
are as follows:

     Composition of the Fuel

          FFC = Fuel fraction carbon by weight
          FFH = Fuel fraction hydrogen by weight
          FFO = Fuel fraction oxygen by weight
          FFX = Fuel fraction of other elements by weight
     The following is based on 86.144-78  Calculations; exhaust emissions.

     The final reported test results shall be computed by use of the following
formula:

     (a)  For light-duty vehicles and light-duty trucks:

     Ywm = -43(/(Dct + Ds + -57Yht + V/2,
           CC>2 in grams per vehicle mile.
     Yct = Mass emissions as calculated from the "transient" phase of the
           cold start test, in grams per test phase.
     Y^t = Mass emissions as calculated from the "transient" phase of the
           hot start test, in grams per test phase.
     Ys  = Mass emissions as calculated from the "stabilized" phase of the
           cold start test, in grams per test phase.
     Dct = The measured driving distance from the  "transient" phase of the
           cold start test, in miles.
     D*. = The measured distance from the "transient" phase of the hot
           start test, in miles.
     Ds  = The measured driving distance from the  "stabilized" phase of
           the cold start test, in miles.
                                     12

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     (b)   The mass of each pollutant for each phase of both the cold start
test and the hot start test is determined from the following:

 (1)  Organic matter mass  (to be calculated individually for  each major
     component of organic matter in the exhaust) .
     OMmasS = vmixXDensityOMx(OMconc/1'000'000)

 (2)  Oxides of nitrogen mass:
     N0xmass = VmixxDensityNOxxKHx(NOxconc/l,000,000)

 (3)  Carbon monoxide mass:
     C0mass = Vx^^i^CO^^conc/1'00

 (4)  Carbon dioxide mass:
     cmass = VmixXDensityC02X (C02conc/10)
      (c)  Meaning of symbols:

 (1)  OMmas  ~ Organic matter emissions, in grams per test phase.
    *Density   = 14.135/EFC g/ft3 (0.4493/EPC kg/m3)*

     Based on:  Density of hydrocarbons is 16.33 g/ft3(0.5768 kg/m3),
assuming an average carbon-to-hydrogen ratio of 1:1.85, at 68F(20C)
and 760 mm Hg  (101.3 kPa) pressure.

     Where :
    *EFC = Fraction carbon in exhaust organic matter.

    *OMCQnc =  Organic matter concentration of the dilute  exhaust  sample
     corrected for background in ppm carbon equivalent.

     Where :
     *OM     = OM  - OM, (1-1/DF)*
        cone     c     d

     Where:
     OM  = Organic matter concentration of the dilute  exhaust sample or, for
           Diesel, average organic  matter  concentration of dilute  exhaust
           sample as calculated from the integrated OM traces, in ppm
           carbon equivalent.

     01% = Organic matter concentration of the dilution air  as measured, in
           ppm carbon equivalent.*

(2)  NOxmass = Oxides of nitrogen  emissions, in grams per test phase.

     DensityNO2 = Density of oxides of nitrogen is 54.16  g/ft3 (1.913 kg/m3)
     assuming they are in the form of nitrogen dioxide, at 68F(20C) and
     760 mm Hg (101.3 kPa)  pressure.
                                     13

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    NO      = Oxides of nitrogen concentration of the dilute exhaust sample
    corrected for background, in ppm.

    N0xconc = Nxc - N0xd(l - 1/DF)

    Where:
    NOjj = Oxides of nitrogen concentration of the dilute exhaust sample
          as measured, in ppm.

    NOX(j = Oxides of nitrogen concentration of the dilution air as measured,
           in ppm.

(3)  COmass = Carbon monoxide emissions, in grams per test phase.

    Densityco = Density of carbon monoxide is 32.97 g/ft^d.164 kg/m ),
    at 68F(20C) and  760 mm Hg  (101.3 kPa) pressure.

    C0conc = Carbon monoxide concentration of the dilute exhaust sample
    corrected for background, water vapor, and CO2 extraction, in ppm.

    C0conc = C0c - cdd - 1/DF)

    Where:
    *COC = Carbon monoxide concentration of the dilute exhaust  sample
          volume  corrected for water  vapor and carbon dioxide  extraction,
          in ppm.*

    *COC =  (1 -  (0.01  + 0.005XHCR)  C02c -  0.000323R) CO^*

     Where:

            measured,  in ppm.
COcm = Carbon monoxide concentration of the dilute exhaust sample as
     c2c = Carbon dioxide concentration of the dilute exhaust sample,
            in percent.

     R = Relative humidity of the dilution air, in percent (see 86.142(n)).

    *HCR = Hydrogen-to-carbon ratio of the fuel
         = (FFH/1.008)/(FFC/12.011)*

     C0d = Carbon monoxide concentration of the dilution air corrected
           for water vapor extraction, in ppm.

     C0d = (1 - 0.000323R)COdm

     Where:
     COj- = Carbon monoxide concentration of the dilution air sample as
            measured,  in ppm.
                                     14

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     Note:  If a CO instrument which meets the criteria specified in 86.111
is used and the conditioning column has been deleted, CO   can be substitute
directly for COC and CO^ can be substituted directly for C0d.

(4)   C2mass = Carbon dioxide emissions, in grams per test phase.

     DensityCQ2 = Density of carbon dioxide is 51.81 g/ft^ (1.830 kg/m-^) ,
     at 68F(20C) and 760 mm Hg(101.3 kPa)

     C2conc= Carkn dioxide concentration  of the dilute exhaust sample
     corrected for background, in percent.

     C02conc = C02C - C02d (1 - 1/DF)

     Where:
     C02d = Carbon dioxide concentration of the dilution air as measured,
            in percent

(5)  *DF = SPC02/[C02c +  (OMC + COC)10~4]*

     Where:
    *SPCO2 = Stoichiometric percent of C02 in undiluted exhaust
           = (FFC/(FFC + 5.958 FFH + 12.01P
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     vmix = Total dilute exhaust volume in cubic feet per test phase
            corrected to standard conditions: of 528F (293K) and 760
            mm Hg (101.3 kPa) .

     For PDF - CVS, Vmix is:
     V .   = V xN(PB - P4) 528 R
     vmin   vo  (760 mm Hg)  (Tp)

     for SI units ,


     V    = v XN(PB - P4)(293.15 K)
      mix       (101.325 kPa) (TD)

     Where :
     V0 = Volume of gas pumped by the positive displacement pump,  in  cubic
          feet  (m3) per revolution.  This volume is dependent  on the
          pressure differential across the positive displacement pump.
     N  = Number of revolutions of the positive displacement pump  during
          the test phase while samples are being collected.
     PB = Barometric pressure, in mm Hg  (kPa) .
     Pd = Pressure depression below atmospheric measured  at the inlet to
          the positive displacement pump, in  mm Hg  (kPa)  (during an Idle
          mode) .
     Tp = Average temperature of dilute exhaust entering  positive
          displacement pump during test, R(K) .

     (d)   Example calculation of mass values  of exhaust emissions  using
positive displacement pump and Indolene fuel  of CH1>85.  For Indolene Fuel,
the exhaust organic matter are hydrocarbons) .

(1)  For the "transient" phase of the cold start test  assume the following:
     V0 = 0.29344 ft3/revolution; N = 10,485; R = 48.0 percent;
     Ra = 48.2 percent; PB - 762 mm Hg; Pd =  22.225 mm Hg; P4  = 70 mm Hg;
     Tp = 570 R; HCC = 105.8 ppm, carbon equivalent; NOXC = 11.2 ppm;
     C0cm = 306.6 ppm; CLC = 1.43 percent; HCd = 12.1  ppm; NOxd =  0.8 ppm;
     codm =15-3 ppm.

          c2d = 0.032 percent; Dct = 3.598 miles;

    *FFC = 0.8656; FFH = 0.1344;
     FFO = 0; FFX = 0; FID Response Factor =  1.0.*

     Then:
     Vm.   =  (0.29344)x(10.485)x(762 - 70)x
      IFl-L .X                                -^           ,
             (528)/(760) (570) = 2595.0 ft3 per test  phase.

     H    =  (43.478)  (48.2)  (22 . 225) / [782 -  (22.225X48.2/100))]
          = 62  grains of water per pound of  dry  air.

     KH =  1/[1  - 0.0047(62  -75)] = 0.9424


                                     16

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    *HCR = (0.1344/1.008)/(0.8656/12.Oil) = 1.85*

    *COC = (1 - (0.01 + 0.005X1.85)1.43 - 0.000323X48)306.6 = 293.4 ppm

     C0d = (1 - 0.000323X48)15.3 = 15.1 ppm

    *SAFR = 11.514XQ.8656 + 34.298XQ.1344 = 14.576*

    *SPC02 =  (0.8656/(0.8656 + 5.958XQ.1344 + 0.3278X14.576))xiQO = 13.4*

    *DF  = 13.4tl.43 + (105.8/1.0 + 293.4)xiO~4] = 9.116*

    *HCCC = 105.8 - 12.1(1 - 1/9.116) + 95.03 ppm.*

    *HCconc = HCcc/1'0 = 95'03 PPm*

    *Density HC = 14.135/0.8656 = 16.33 g/ft3*


     HCmass = (2595)(16.33)(95.03/1,000,000) = 4.027 grams per test phase

     NOxconc = 1;L-2 ~ 0.8(1 - 1/9.116)  = 10.49 ppm

     NOxmass = (2595)(54.16)(10.49/1,000,000)(0.9424) = 1.389 gram per test phase.

     cor,r-  = 293.4 - 15.1(1-1/9.116)  = 280.0 ppm
       con c

     C0mass  = (2595) (32.97) (280/1,000,000)  = 23.96 grams per test phase

     C02conc = 1.43 - 0.032(1 - 1/9.116)  = 1.402%

     C02mass = (2595.0)(51.85)(1.402/100) = 1886 grams per test phase.

(2)   For the stabilized portion of the cold start test assume that similar
calculations resulted in the  following:

     HCmass  = 0.62 grams per test phase

     NOxmass = 1.27 grams per test phase

     COmass  = 5.98 grams per test phase

     c2mass = 2346 grams per test phase

     Ds      = 3.902 miles
                                     17

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(3)   For the "transient" portion of the hot start test assume that similar
calculations resulted in the following:

     HCmass  = 0.51 grains per test phase

     NOxmass = 1.38 grams per test phase

     COmass  = 5.01 grams per test phase

     c2mass = 1758 grams per test phase

     Dht     = 3-598 miles

(4)   Weighted mass emission results:

     HCwm  = 0.43[(4.027 + 0.52)/(3.598 + 3.902)] + 0.57[(0.51 + 0.62)/
             (3.598 + 3.902)] = 0.352 grams per vehicle mile.

     N0xwm = 0.43[(1.389 + 1.27)7(3.598 + 3.092)] + 0.57[1.38 + 1.27)/
              (3/598 + 3.902)] = 0.354 grams per vehicle mile.

     CO^  = 0.43[(23.96 + 5.98)/(3.598 + 3.902)] + 0.57[5.01 + 5.98)/
              (3.598 + 3.902)] = 2.55 grams per vehicle mile.

     C02wm = 0.32 [(1886 + 2346)/(3.598 + 3.902)] + 0.57  [(1758 + 2346)/
              (3.598 + 3.902)] = 555 grams per vehicle mile

    *(e)  Example calculation of mass values of exhaust emissions when using
methanol fuel  (CH4O).  All inputs except for fuel composition and exhaust
organic matter are assumed  to be the  same as  in  previous  example  (d).

(1)   Fuel composition is as  follows:

     FFC = 0.375; FFH = 0.126; FFO = 0.499;


     Then:
     Vmix =  2595' ft3

     KH   =  0.9424

     HCR  =  (0.126/1.003)/0.375/12.Oil) = 4.00

     COC  =  (1 -  (0.01 + 0.005X4.00)1.43 - 0.000323X48)306.6  = 288.7 ppm

     C0d  =  15.1 ppm
                                     18

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SAFR = 11.514X0.375 + 34.298X0.126 - 4.322XQ.499 =  6.48



SPCO2 = (0.275/(0.375 + 5.958X0.126 + 0.3278X6.482))xiQO  =  11.54



(OMC by FID)/(C02c + COC) = 105.8/(1.43X104 +  288.7) = 0.007<0.02.



Therefore:



DF = 11.54/[1.43 +  (105.8 + 288.7)X10~4] = 7.84



DensityQM = 14.135/0.375 = 37.69 g/ft3



OM     =  (Data are not available)
  cone


OM     =  (can not be determined from available data)
  mass


(OM     by FID = (2595)(37.69)(105.8/1,000,000) = 10.35 grams  per test phase).
   IllciSS


        = 11.2 - 0.8(1 - 1/7.84) = 10.50 ppm



Nxmass = (2595)(54.16)(10.51/1,000,000)(0.9424) =  1.391  grams per  test phase.



CO     = 288.7 - 15.1(1 - 1/7.84) = 275.5 ppm
  cone


CO     =  (2595) (32.97) (275.5/1,000,000) = 23.57 grams per test phase.
  mass


c2conc = i-43 ~ 0-032(1 - 1/7.84) = 1.402%



c2mass = (2595.0)(51.85)(1.402/100) = 1886 grams per test  phase.*
Assume 100.0 ppm of methanol was measured in the  exhaust using  the method

given in Appendix A-5:



Methanol     =  (2595) (37.69) (100.0/1,000,000) = 9.781  gram  per  test  phase
        rricis s




Note:  Other components of organic matter may also be  present in  the

       exhaust; these should be determined and reported to  the  extent

       practical.
                                19

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C.   Calculation of Particulate Exhaust Emissions

     Use of an alternate fuel does not affect the procedure or the calculations
for diesel particulate emissions.  Therefore, the procedure and the calculations
for diesel particulate given in 40 CFR, Part 86, Subpart B can be used, without
modification.
D.   Non-Methane Hydrocarbons

     Consideration has been given by the EPA to basing the HC emissions
standard on non-methane hydrocarbons.  This, however, has not been done,
but remains under consideration.  Therefore, for the present, it is recom-
mended that the composition of the exhaust HC be defined to the extent
practical (e.g., with methanol fuel, measure exhaust for methanol, aldehydes,
and methane).  Such data could provide input for future decisions as more
becomes known about individual hydrocarbon photochemical reactivity.

E.   Unregulated Exhaust Emissions

     It has been determined that some alternate fuels may be prone to produce
higher levels of some currently unregulated emissions  (e.g., alcohol fuels
tend to produce higher levels of aldehydes).  At the present time, the only
specific recommendation is to include the analyses of aldehydes and the
specific alcohol, when an alcohol fuel is used.

     Other  emissions to measure for, if any, should be based on the compo-
sition of the fuel and on whichever emission(s) is  (are) considered to be
of sufficient importance at the time.  No specific recommendations can be
provided, but some general guidance can be  given.  Under certain operating
conditions  the following relationships might occur:
Fuel Description

Methanol


Ethanol


High sulfur
 High aromatic
 (diesel)
 High Nitrogen
 (diesel)
Other Exhaust Emissions to Consider

aldehydes (primarily formaldehyde)
unburned methanol

aldehydes (primarily acetaldehyde)
unburned ethanol

sulfate
sulfur dioxide

phenols
nitropyrenes
Ames response

nitropyrenes
Ames Response
 Source for
 Analytical
   Method

Appenidx A-4
Appendix A-5

Appendix A-4
Appendix A-6

Reference 3
Refreence 3

Reference 7
Reference 8
Reference 9

Reference 8
Reference 9
                                     20

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                              V.  FUEL ECONOMY
     The procedure for determination of fuel economy, given in the fuel
Economy Regulations,'  '  can be made applicable for use with alternate
fuels by incorporating the actual carbon fraction and density of the fuel.
For alternate fuels, however, the resulting expression of fuel economy,
in terms of distance traveled per unit volume of fuel used, is not
sufficient to enable making meaningful comparisons.  Therefore, an addi-
tional method for expression of fuel economy (consumption) has been selected
and its use is recommended.

 A.  Calculation of Fuel Economy

     The following calculations for fuel economy are recommended for use when
 non-standard carbon containing fuels are utilized.  These calculations are
 based on the method given in 40 CFR Part 600, Subpart B,  600.113-78  and
 Appendix II, with latest revisions incorporated.  The basic format used in
 600.113 has been, retained.  Changes or additions to the  calculation
 method in 600-113-78 are identified by asterisk(*).  A required analysis,
 in addition to those required in 600.113 or in the previous calculation
 procedure for exhaust emissions given in Section IV of this report, is
 the density of the fuel.

     The following is based on 600-113-78 Fuel economy calculations.

    *The calculations of vehicle fuel economy values require the weighted
 grams/mile values for OM, CO, and CO2-  (OM = Organic matter).*

    *(a) Calculate the weighted grams/mile values for the  city fuel economy
 test for OM, CO, and C02 as specified in the modifications to 86.144 as
 given in Section IV.B.  of this report.*

    *(b)(1)  Calculate the mass values for the highway fuel economy test
 for OM, CO, and CO2 as specified in modifications to paragraph (b) of
 86.144 as given in Section IV.B. of this report.*

        (2)  Calculate the grams/mile values for the highway test for  OM, CO,
 and CO2 by dividing the mass values obtained in (b)(1) by the actual
 distance traveled, measured in miles, as specified in paragraph  (h) of
 86.135.

      (c) Calculate the city fuel economy and highway fuel economy from grams/
 mile values for OM, CO, and C02.  The OM values (obtained per paragraph  (a)
 or (b) as applicable) used in each calculation in this section are rounded
 to the nearest 0.01 grams/mile.  The CO values  (obtained per paragraph (a)
 or (b) as applicable) used in each calculation in this section are rounded
 to the nearest 0.1 grams/mile.  The CO2 values  (obtained per paragraph (a)
 or (b) of this section as applicable) used in each calculation in this
 section are rounded to the nearest gram/mile.

                                     21

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   *(d) and  (e)  Calculate the fuel economy in miles per gallon of gasoline
by dividing the grams of carbon per gallon of fuel  (GCPG) by the sum of
three terms:*

   *Where:  GCPG = 3785.4XFFCXFDEN

   *Where:  FFC  = Fuel Fraction Carbon
            FDEN = Fuel Density, g/m

   *Note:   GCPG is equal to 2421 for certification gasoline and 2778 for
            certification diesel fuel.*


   *(1)  OMFC multiplied by OM (in grams/mile as obtained in paragraph (c)).*

     (2)  0.429 multiplied by CO (in grams/mile as obtained in paragraph  (c)), and

     (3)  0.273 multiplied by CO2 (in grams/mile as obtained in paragraph (c)).

   *Where:   OMFC is the fraction carbon in the exhaust organic  matter.
            [If OMC by FID divided by (CO2C + COC)  is  less than 0.02,  the
            FID measured value can generally be used for OMC.   Also,  it
            can be assumed that OMFC = FFC].


    Round the quotient to the nearest 0.1 mile per gallon.

    The following is based on Appendix II - Sample Test Value Calculation

     (a)  Assume that a gasoline-fueled vehicle was tested by the Federal
Emission Test Procedure and the following results were calculated:

    HC  = 1.03 grams/mile
    CO  =6.74 grams/mile
    CO2 = 785 grams/mile

   *According to the preceding  procedure, the fuel economy or MPGC for the
    vehicle may be calculated by substituting the HC, CO and CO2 grams/mile
    values into the following equation.*

   *MPGC = GCPG/(HCFC>
-------
     (b)  Assume that the same vehicle was tested by  the Federal  Highway  Fuel
Economy Test Procedure and a calculation similar to  that  shown in  (a)
resulted in a highway fuel economy of MPG^ of 18.6.  According to  the pro-
cedure in 600.113, the combined fuel economy  (called MPGc/v.) for  the
vehicle may be calculated by substituting the city and highway fuel  economy
values into the following equation:

    MPG /,  = 1/(0.55/MPGC + 0.45/MPGh)
        '  = 1/(0.55/11.1 + 0.45/18.6) =
    MPGc/h =13.6 MPG
    *(c)  Assume that  a methanol-fueled vehicle was  tested  and  the  same  emission
 results were obtained (OM = 1.03 grams/mile).

    Then:  FFC = 0.375
           FDEN = 0.7914 g/m

    GCPG = 3785.4XO.375XQ.7914 = 1123
    OMPC = FFC = 0.375

    MPG  = 1123/((0.375X1.03) +  (0.429X6.74)  +  (0.273X785)
         = 1123/217.6 = 5.2 MPG*

B.  Fuel Economy Related Considerations

    There are several potentially important additional fuel economy related
considerations.

    Energy Based Fuel Consumption - Alternate fuels can have a greatly dif-
ferent energy content per unit of volume and weight than is contained in cur-
rent petroleum fuels.  Therefore, fuel economy (or consumption) expressed only
in miles per gallon (/100 km)  can present a distorted picture of the actual
fuel energy consumed.  Fuel consumption expressed in terms of Btu per mile
 (j/km) can provide potentially useful information regarding the actual fuel
energy consumed.  Therefore,  it is recommended that fuel consumption be
expressed in Btu per mile, in addition to expressing fuel economy in miles
per gallon.  The calculation for energy based fuel consumption, derived in
Appendix C-l, is as follows:

         EBFC = 8.34XLHVXFDEN/FE

         Where:
             EBFC = Energy Based Fuel Consumption, Btu/mi
             LHV  = Fuel Lower Heating Value, Btu/lb
             FEDN = Fuel Density, g/m
             FE   = Fuel Economy, mpg
                                    23

-------
    Effect of Particulate Emissions - The fuel economy calculation in
Subpart B does not account for the carbon in the particulate emissions.
With a standard hydrocarbon diesel fuel and particulate emissions below
0.6 g/mi, the effect of the particulate emissions on the calculated fuel
economy is considered to be negligible.

    The effect of the particulate emissions on the calculated fuel economy
can be determined as follows:

         MPGW = MPG/(1 + 0.00036XPart.xpFCXMPG)

         Where:
             MPGW  = Calculated miles per gallon with particulate
                     emissions included
             MPG   = Calculated miles per gallon using the method
                     in 600.113-78
             Part. = Particulate emissions rate in g/km
             PFC   = Mass fraction of carbon in the particulate

    Example values are given as follows:

               Particulate     Calculated Fuel Economy, mpg
             Emissions, g/mi       MPG       MPGy,

                   0.2              25       24.9
                   0.2              50       49.8

                   0.6              25       24.8
                   0.6              50       49.5

    For  alternate fuels, the expression of fuel economy in terms of distance
traveled per unit volume of fuel used may not  always be sufficient to  enable
making meaningful comparisons.

    Other Considerations - For additional discussion of methods  for expressing
fuel  economy, the reader is referred to Reference  2.
                                     24

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                        VI.  EVAPORATIVE EMISSIONS
    Calculation of a mass value for evaporative emissions requires knowing
the molecular weight per carbon atom of the emissions.  The calculation
method given in the light-duty certification procedure uses molecular weights
derived from empirical data. '^'  Those molecular weights, however, are only
applicable to gasolines meeting the prescribed fuel specifications.  There-
fore, for alternate fuels, molecular weights have to be determined or satis-
factorily estimated.  Derivations of equations are given in Appendix C-2.

A.  Evaporative HC Composition for Hydrocarbon Fuels

    Detailed analyses for the composition of the evaporative hydrocarbon
emissions is extremely difficult, and is considered to be an impractical
requirement in the routine determination of evaporative emissions for
experimental blends of hydrocarbon fuels.  Therefore, assumption and methods
for estimation of the composition of the evaporative HC emissions are given
for various categories of such fuels as follows:

    Standard Cuts of Hydrocarbon Fuels - Standard fuel cuts, containing
hydrocarbons composed of carbon and hydrogen (at least ninety-nine percent)
and providing for acceptable vehicle performance, would be expected to
have reasonably similar distribution of hydrocarbon types regardless of
the basic source of the fuel.   For such fuels,  the value of the molecular
weight can be assumed to be the same value as used for certification
gasoline.

    Nonstandard Cuts or Blends of Hydrocarbon Fuels - For blends of indivi-
dual hydrocarbons, these components could be analyzed for in the evaporative
emissions using GC.  For nonstandard cuts and for unknown blends, however,
it will generally be necessary to estimate the composition of the evaporative
emissions.

    The extremes of the hydrogen-to-carbon ratios for hydrocarbons, that could
be in gasoline or otherwise used as fuel, range from 1:1 (benzene) to 4:1
(methane).  This results in extremes in the K value of 2.7 and 3.3.  (The K
value is equal to 0.208 times the molecular weight per carbon atom of the fuel
and is used in the calculation of evaporative emissions.  With the K value
approaching 3.3, it is likely that the constituents would be known or could
be readily determined.  In all likelihood, the K value for a liquid hydrocarbon
fuel consisting of essentially all carbon and hydrogen would be equal to or
only slightly lower than 3.0.   Therefore, for all liquid hydrocarbon fuels
for use in gasoline engines, it is recommended that the K values for certifi-
cation gasoline be used.  For gaseous hydrocarbon fuels, it is recommended
that the K value be determined using GC analyses of the evaporative hydro-
carbon emissions  (as an alternative a K value derived from the fuel constituent
having the highest H/C ratio could be used).
                                    25

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B.  Evaporative Organic Matter Composition for Other Fuels

    The only method found to be generally acceptable for determination of
evaporative organic matter composition with alternate fuels is to measure
the individual evaporative components.  The evaporative emissions should
then be computed and reported separately for each of the major components.

C.  Calculation of Evaporative Emissions

    The following calculations for evaporative emissions are recommended
for use when nonstandard carbon containing fuels are utilized.  These cal-
culations are based on the method given in 40 CFR Part 86, Subpart B,
86.143-78, with latest revisions incorporated.  The basic format used in
86.143 has been retained.  Changes or additions to the calculation method
in 86.143-78 are identified by asterisk(8).

    The following is based on 86.143-78 Calculations; evaporative emissions,

    The calculation of the net hydrocarbon mass change in the enclosure is
used to determine the diurnal and hot soak mass emissions.  The mass is
calculated using initial and final hydrocarbon concentrations in ppm carbon,
initial and final enclosure ambient temperatures, initial and final baro-
metric pressures, and net enclosure volume using the following equation:

     Cn  = kV xio"4 |COMfPBf   COMiPBi I
           -      L~T1
    Where:

    MOM = organic matter mass, g
    COM = organic matter concentration as ppm carbon
   *V   = net enclosure volume, ft3(m3) as determined by subtracting
               "3        "3
          50 ftj  (1.42 mj) or an approved measured volume,  (volume of
          vehicle with trunk  and windows open) from the enclosure
          volume.*
    PB  = barometric pressure, in Hg  (kPa)
    T   = enclosure ambient temperature, R(K)
    i   = indicates initial reading
    f   = indicates final reading.

    K   = 0.208x(Mol. wt. per carbon atom)
          for SI  units, K = 1.2*(Mol. Wt. per C)

    For Certification Gasoline:

         K = 2.98(17.2) for diurnal emissions, (MW/C = 14.33)
         K = 2.95(17.0) for hot soak emissions,  (MW/C = 14.18)

   *For Other Fuels:

         Molecular Weight per carbon atom is to be determined.*

    The reported results shall be computed by summing the individual evapo-
rative emission results determined in the diurnal breathing-loss test,  the
running-loss test, and the hot-soak test.

                                    26

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                                  REFERENCES
 1.   Code of Federal Regulations,  Title 40, Chapter 1, Part 86,  Subpart B.

 2.   Harvey, Craig A.,  "Gasoline-Equivalent Fuel Economy Determined for
      Alternate Automotive Fuels,"  SAE Paper 820794, 1982.

 3.   Dietzmann, Harry E., et al, "Analytical Procedures for Characterizing
      Unregulated Pollutant Emissions from Motor Vehicles," Final Report
      EPA 6OO/2-79-017,  February 1979.

 4.   Methane Measurement  Using Gas Chromatography,  SAE JllSla,  Published
      in the 1980 SAE Handbook.

 5.   Smith, Lawrence R. and Urban,  Charles, "Characterization of Exhaust
      Emissions from Methanol and Gasoline Fueled Automobiles,"  Final
      Report EPA 460/3-82-004,  March 1982.

 6.   Bykowski, Bruce B.,  "Gasohol,  TEA, MTBE Effects on Light-Duty Emissions,"
      Final Report of Task No.  6 of EPA Contract 68-03-2377,  October 1979.


 7.   Dietzmann, Harry E., et al, "Analytical Procedures for Characterizing
      Unregulated Pollutant Emissions from Vehicles  Using Middle-Distillate
      Fuels," Interim Report EPA-600/2-80-068, April 1980.

 8.   Tejada, Silvestre  B., et al,  "Analysis of Nitroaromatics in Diesel
      and Gasoline Emissions,"  SAE  Paper 820775.

 9.   Ames, B., et al, "Methods for Detecting Carcinogens and Mutagens
      with the Salmonella/Mannalian-Microsome Mutagenicity Test."
      Mutation Research,  31, pp, 347-364,  1975.

10.   Code of Federal Regulations,  Title 40, Chapter 1, Part 600, Subpart B.


11.   Weast, Robert C.,  Ph.D.,  "Handbook of Chemistry and Physics," 54th
      Edition, CRC Press,  1974.
                                      27

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                            SELECTED BIBLIOGRAPHY
     A number of other sources of information, although not directly
utilized in this report, had an influence on the selection of the specific
methods recommended and on the comments provided in this report.


Furey, Robert L., and King, Jack B., "Evaporative and Exhaust Emissions from
Cars Fueled with Gasoline Containing Ethanol or Methyl tert-Butyl Ether,"
SAE Paper 800261.

Espinola, Stephen A., and Pefley, Richard K.,  "Alternate Fuel Influences
on Emissions Test Procedures," Paper to be presented at the American Chemical
Society Symposium on "Chemistry of Oxygenates in Fuel,"  September 12-17/1982.


Wagner, T. O., et al. "Practicality of Alcohols as Motor Fuels," SAE
Paper 790429.

Lawrence, D.C.,  and Niemczak, D.J., "Evaporative and Exhaust Emissions of
Two Automobiles  Fueled with Volatility Adjusted Gasohol," Paper EPA-AA-
TED-81-12, December 1980.

Lang, J. M., and Black, F. M., "Impact of Gasohol on Automobile Evaporative
and Tailpipe Emissions," SAE Paper 810438.

Dir-itriades, B., and Joshi, S. B., "Application of Reactivity Criteria in
Oxidant-Related Emission Control in the USA,"  International Conference
Report EPA 600/3-77-OOlb, January 1977.

Memorandum from Frank Black, Chief, ETCS to Karl Hellman, Chief, CTAB,
"Emissions and Fuel Consumption Measurements with Alternate Fuels,"
September 24, 1981.

Lawrence, Richard, "Fuel Economy Measurement Carbon Balance Method,"
Draft Report, October 1981.

California Air Resources Board, "Alcohol Fueled Fleet Test Program,"
Project 3T8001,  Second Interim Report, July 1981.

Alson, Jeff, "A Brief Summary of the Technical Feasibility, Emissions and
Fuel Ecnoomy of  Pure Methanol Engines," Technical Report EPA-AA-SDSB-82-1,
December 1981.

California Air Resources Board, "Fuel Economy Calculations for LPG Based
on the Cold Start CVS-1975 Federal Test Procedure," Proposed amendments
transmitted by letter dated August 3, 1982.

California  Air  Resources  Board,  "California Exhaust Standards and Test
Procedures  for  Systems  Designed  to Convert  Motor Vehicles  to Use Alcohol
or  Alcohol/Gasoline  Fuels,"  Proposed procedure  received  in September  1982.


                                     28

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                                 APPENDICES

                  A.  APPENDICES FOR SECTIONS I THROUGH III

                  B.  APPENDICES FOR SECTION IV

                  C.  APPENDICES FOR SECTIONS V AND VI
NOTE:  The format used for mathematical equations is in accordance
       with that used in the Code of Federal Regulations.^)
       Computations are to be performed in accordance with the
       IBM hierarchy of operations.

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                   APPENDIX  A
A-l.  CVS FLOWRATE DETERMINATION
A-2.  DERIVATION OF C02  CONCENTRATION ESTIMATION
A-3.  DETERMINATION OF FID  RESPONSE FACTOR
A-4.  MEASUREMENT OF ALDEHYDES AND KETONES
A-5.  MEASUREMENT OF METHANOL
A-6.  MEASUREMENT OF ETHANOL

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                                 APPENDIX A-l

                         CVS FLOWRATE DETERMINATION
System H20 Capacity = CVSFRXDENAIRx(SatSH - TestSH), wt/time

Where:
     CVSFR  = CVS flowrate, scfm
     DENAIR = Density of air = 0.075 Ib/scf
     SatSH  = Saturation specific humidity, Ib/lb
     TestSH = Specific humidity at test conditions, Ib/lb

Fuel H20 Addition = FCXFFHXIS.016/2.016, wt/time

Where:
     FC  = Fuel Consumption in Ib/min
         = l/MPGXAvg.MPH/6QX8.34XFDEN
     FFH = Fuel fraction hydrogen
     MPG&MPH = Mile per gallon and per hour
     FDEN = Density of the fuel, g/m

Then:
     CVSFRXQ.075(SSH - TSH) = AMPH/MPGXFDENXFFRXl.24
     CVSFR = 16.56XAMPHXFDENXFFN/(MPG  (SSH - TSH))
                                     A-2

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                                 APPENDIX A-2
                 DERIVATION OF CO  CONCENTRATION ESTIMATION
CO % = (MRCO /MRAIR)x(MWAIR/MWCO  )X100

Where:

     MRCO  = Mass flowrate of CO
           = 1/FEXAMPHX8.34XFDENX (44.011/12.01D/60
           = 0.14XAMPHXFDEN/FE

     Where:  FE   = Fuel economy, mpg
             AMPH = Average speed for the  test  cycle,  mph
             FDEN = fuel density, g/m

     MRAIR = 0.075XCVSFR

     Where:  CVSFR = flowrate of the CVS,  scfm

     MWAIR = 28.966
     MWC02 = 44.011

CO % = (0.514XAMPHXFDEN/FE)/(0.075XCVSFR)X(28.966X44.011)X100
     = (451XAMPHXFDEN)/(FEXCVSFR)
                                     A-3

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                                 APPENDIX A-3

                    DETERMINATION  OF  FID RESPONSE FACTOR
     For determination  of  the  response  factor of a specific FID hydrocarbon
analyzer, with a  liquid fuel,  a  standard of known concentration is prepared
using the apparatus shown  in Figure  A-l.  (Figure A-l was adapted from
SAE Paper 810438).
                 Pump   Metering
                 ~     valve
                                    Septum injector
                                             150C
           Figure 1.  Apparatus for preparation of  calibration  mix


In preparing this standard, a known volume  of  the  fuel of interest is
injected, using a microliter syringe,  into  the heated mixing zone (150C)
of the apparatus.  The liquids are vaporized and swept into a Tedlar bag
with a known volume of air measured by a  dry test meter.   The concentration
of the fuel (in ppm C) in the bag is determined as  follows:

FCONC = FINJXFDEN/AIRVXIOOO

Where:
     FCONC = Concentration of the fuel, yg/m
     FINJ = Volume of fuel injected, y
     FDEN = Density of the fuel, g/m
     AIRV = Volume of air, m3 (scfmXQ.02832)

FPPMC = FCONCXQ.02406/FMWC
Where:
     FPPMC
     0.02406
     FMWC
 Fuel concentration as ppmC
Volume in m3 of one mole at 29.92 in. Hg and  68F
Fuel molecular weight per carbon atom
Note:  It is recommended that the response  factor  of the  FID analyzer
       be determined at several concentrations  in  the range  of the
       concentrations in the exhaust samples.
                                     A-4

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     For gaseous fuels, the standards can be prepared using a precision
proportioning system or any other available method that provides accurate
volume measurements of the blending gases.  For gaseous fuels:

GFPPMC = GFVOLXCPM/(AIRV + GFVOL)X106

Where:
     GFPPMC = ppmC of the gaseous fuel
     GFVOL  = Volume of the gaseous fuel
     AIRV   = Volume of air
     CPM    = Carbon atoms per molecule

     The calibration sample is evaluated using the FID analyzer and the FID
response factor is determined as follows:

FIDRF = FIDPPM/FPPMC

Where:
     FIDRF  = Response factor for the FID
     FIDPPM = ppmC value as read on the FID
     FPPMC  = Actual fuel concentration as ppmC

Example A.  Assume a gasoline with a density of 0.739 g/m and a fuel
            fraction carbon of 0.8656.

     FMWC = 1/0.8656X12.011 = 13.86

     Let:  FINJ =1.00
           AIRV = 1 scfm = 0.02832 m

     Then:  FCONC = 1.00XQ.739/0.02832X1000 = 26,095
            FPPMC = 26,095X0.02406/13.86 = 45.4

     Let:  FIDPPM = 45.4

     Then:  FIDRF = 45.4/45.4 = 1.00

Example B.  Assume methanol is used as the fuel.

     FMWC = 32.04
     FDEN = 0.7914 g/mii

     Let:  FINJ = 1.00 )J
           AIRV = 1 scfm = 0.02832 m

     Then:  FCONC = 1.00XQ.7914/0.02832X1000 = 27,945
            FPPMC = 27,945X0.02406/32.04 = 21.0

     Let:  FIDPPM = 17.4

     Then:  FIDRF = 17.4/21.0 = 0.83
                                     A-5

-------
                                APPENDIX A-4

                    MEASUREMENT OF ALDEHYDES AND KETONES
     The measurement of aldehydes (formaldehyde, acetaldehyde, isobutyral-
dehyde, crotonaldehyde, hexanaldehyde,  and benzaldehyde)  and ketones
(acetone and methylethylketone)  in exhaust is accomplished by bubbling the
exhaust through glass impingers containing 2,4 dinitrophenylhydrazine (DNPH)
in dilute hydrochloric acid.  The exhaust sample is collected continuously
during the test cycle.  The aldehydes and ketones (also known as carbonyl
compounds) react with the DNPH to form their respective phenylhydrazone de-
rivatives .  These derivatives are insoluble or only slightly soluble in the
DNPH/HCl solution and are removed by filtration followed by pentane extrac-
tions.  The filtered percipitate and the pentane extracts are combined and
then the pentane is evaporated in a vacuum oven.  The remaining dried ex-
tract contains the phenylhydrazone derivatives.  The extract is dissolved
in a quantitative volume of toluene containing a known amount of anthracene
as an internal standard.  A portion of this dissolved extract is injected
into a gas chromatograph and analyzed using a flame ionization detector.
The detection limits for this procedure under normal operating conditions
are on the order of 0.005 ppm carbonyl compound in dilute exhaust.

LIST OF EQUIPMENT

     The equipment required for the analysis of aldehydes and ketones is
divided into three groups:  sample acquisition, sample preparation, and
sample analysis.  Manufacturer, stock number and any pertinent descriptive
information are listed.

Sample Acquisition

     1.  Glass impingers, Ace Glass Products, Catalog #7530-11, plain
         tapered tip stoppers with 18/7 arm joints and 29/42 bottle joints.

     2.  Flowmeter, Brooks Instrument Division, Model 1555, tube size
         K-2-15-C, graduated 0-15, sapphire float, 0-5 &/min range.

     3.  Sample pump, Thomas Model 106 CA18, capable of free flow capacity
         of 4 /min.

     4.  Dry gas meter, American Singer Corporation, Type AL-120, 60 CFH
         capacity.

     5.  Regulating valve, Nupro 4MG, stainless steel.

     6.   leflon tubing, Lniued States Plastic Corporation,  1/4" OD x 1/8"
          ID and 5/16" OD  * 1/8" ID.


                                     A-6

-------
     7.  Teflon solenoid valve, The Fluorocarbon Company, Model DV2-144NCA1.

     8.  Drying tube, Analabs, Inc., Catalog #HGC-146, 6" long, 1/4" brass
         fittings.

     9.  Miscellaneous Teflon nuts, ferrules, unions, tees, clamps, connec-
         tors, etc.

    10.  Digital readout for dry gas meter.

    11.  Miscellaneous electrical switches, lights, wirings, etc.

    12.  Six channel digital thermometer, Analog Devices, Model #2036/J/1.

    13.  Iron/Constantan type J single thermocouple with 1/4" OD stainless
         steel metal sheath, Thermo Sensors Corporation.

    14.  Variable autotransformer, Staco Inc., Type 3PN 1010.

    15.  Heating sleeve wrapped with insulation and insulation tape.

    16.  Class A, 20 m volumetric pipets.

    17.  Class A, 1000 m volumetric flask.

    18.  Teflon coated stirring bar.

    19.  Hot plate-stirrer, Corning, PC-351.

Sample Analysis

     1.  Varian 1700 gas chromatograph equipped with dual flame ionization
         detectors in differential operation, and a linear temperature
         programmer.

     2.  Soltec Model B-281 1 mv recorder.

     3.  Hewlett-Packard Model 3354 gas chromatograph computer system with
         remote teletype printout.

     4.  Syringe, 10 m, Hamilton Company, #701.

     5.  Dual columns, 24 x 1/8" OD, stainless tubing packed with 6.7
         percent Dexsil 300 GC on Chromosorb G 60/80 mesh, DMCS treated
         and acid washed.

Sample Preparation

     1.  Fritted glass filters, Ace Glass Company,  porosity D, ASTM 10 - 20
         microns pore size, 24/40 ground glass joint, vacuum takeoff.
                                    A-7

-------
     2.  Constant temperature vacuum oven, National Appliance Company.

     3.  Pump for oven, Thomas Industries, Model 907CA18 2.

     4.  Flasks, 125 m& capacity, 24/40 ground glass joints.

     5.  Separatory funnels, 125 m.

     6.  Separatory funnels, 250 mi.

     7.  Separatory funnel shaker, Burrell Corporation, Wrist-Action(jO
         type with appropriate funnel holders, Model 75.

     8.  Ring stands, labels, holders, tubing, vacuum tubing, fittings
         and clamps needed for equipment manipulation.

     9.  Wash bottles, 500 m.

    10.  Graduated cylinders, 50 mJ,.

    11.  Vials, Kimble, 1/2 dram.

    12.  Vacuum pump, Sargent-Welch.

LIST OF REAGENTS

     A list of the reagents used in the determination of the aldehydes and
ketones in exhaust is provided along with chemical formula, molecular weight,
purity, manufacturer, and catalog number.

     1.  Hydrochloric acid, HC1, 36.46 g/mole, concentrated  (37%), analyt-
         ical reagent, Mallinckrodt, Cat. #2612.

     2.  Pentane, C5H12, 72.15 g/mole, Distilled in glass  (bp 35-37C),
         Burdick and Jackson Laboratories, Inc.

     3.  2,4 DinithrophenyIhydrazine  (2,4-DNPH), (NO2)2C5H3CH=N-NH2,
         210.149 g/mole, Aldrich analyzed, Aldrich, Cat. #D19,930-3.

     4.  Sodium Bicarbonate, NaHCO3, 84.00 g/mole, Mallinckrodt, Cat.  #7412.

     5.  Anthracene, C^H^o/ 178.24 g/mole, K and K Laboratories, Cat.
         #10714.

     6.  Toluene, CgH^CH^, 92.14 g/mole Baker Analyzed Reagent, Baker
         Cat. #3-9460.

     7.  Methylene Chloride, CH2Cl2r 84.93 g/mole, Reagent ACS, Eastman,
         Cat. #13022.

PREPARATION OF ABSORBING SOLUTION
                                    A-8

-------
     To prepare the absorbing solution, 163 mZ of concentrated HCl and 2.5 g
of 2,4-DNPH crystals are added to a one liter volumetric  flask containing
about 500 m& of deionized water.  The flask is diluted to mark and stirred
for several hours at room temperature with an automatic stirrer/teflon
coated stirring bar to dissolve the DNPH.  Fresh absorbing solution is pre-
pared daily as needed.

PREPARATION OF TOLUENE/ANTRACENE SOLUTION

     Toluene containing approximately 0.05rag anthracene per m of toluene
is used to dissolve the dried phenylhydrazone extracts.  This solution is
made by adding 100 mg of anthracene to a two liter volumetric flask and di-
luting to mark with toluene.

PREPARATION OF PHENYLHYDRAZONE DERIVATIVES

     In order to obtain response factors for each of the phenylhydrazone
derivatives to anthracene, pure derivatives were prepared from their re-
spective aldehydes and ketones.  These derivatives were made by adding each
of the carbonyl compounds separately to a 2N HC1-DNPH solution.  The result-
ing orange to red precipitates were filtered and dried.  The derivatives
were then recrystallized from hot absolute ethanal.  The melting points
for each of the derivatives were compared to literature values before use.
A GC trace was also made on each of the derivatives to further check the
purity.

PREPARATION OF STANDARD SOLUTION OF PHENYLHYDRAZONE DERIVATIVES
AND ANTRACENE

     A standard containing the phenylhydrazone derivatives and anthracene
in toluene is prepared to obtain a response factor of each of the deriva-
tives to anthracene.  The solution is made by dissolving weighed amounts
of anthracene and each of the derivatives in a quantitative volume of
toluene.  These solutions contain approximately O.OSmg anthrancene per m&
of toluene and approximately 0.2 mg of each derivative per mH of toluene.

SAMPLING SYSTEM

     Two glass impingers in series, each containing 40 m of   2N HCl-2,4
dinitrophenylhydrazine, are used to collect exhaust samples for the analysis
of the aldehydes and ketones.  A flow schematic of the sample collection
system is shown in Figure 1.  The two impingers together trap approximately
98 percent of the carbonyl compounds.  The temperature of the gas stream
is monitored by a thermocouple immediately prior to the dry gas meter.  The
dry gas meter determines the total flow through the impinger during a given
driving cycle.  The sample pump is capable of pulling a flow rate of 4 Jl/min.
A drier is included to prevent condensation in the pump, flowmeter, dry gas
meter,  etc.  The flowmeter allows continuous monitoring of the sample flow
to insure proper flow rates during the sampling.  The Teflon line connecting
the CVS and the solenoid valve is heated to ^170F in order to prevent
water from condensing in the line.  Several views of the sampling system
are shown in Figure 2.


                                  A-9

-------
                                                                              Gas Temperature
                                                                              Digital Readout
                                                                Sample
                                                                 Pump
I
M
O
                     On-Off
                    Solenoid
                      Valve
                                                                        Regulating
                                                                           Valve
         Dilute
         Exhaust

                 Ice Bath
            Temperature Readout
  Gas Volume
Digital Readout
                             Figure 1.
Aldehyde and Ketone sample collection flow schematic-

-------
                  Front View
                                                      Digital
                                                      Readout
                                                       Flowmeter
                                                       Regulating
                                                       Valve
            Close-Up of Upper Front
Figure 2.  Aldehyde and Ketone sampling system.
                     A-ll

-------
Solenoid
                          Close-up of  Impingers  (Side View)
                                                  Solenoid
                                                  Filter
                                                  Ice Bath
                                                   rier
                                                  Dry Gas Meter

                                                  Pump
               Rear  View
           Figure 2 (Cont'd).   Methanol sampling system.
                               A-12

-------
ANALYTICAL PROCEDURE

     The analysis of the aldehydes  (formaldehyde, acetaldehyde,  iso-
butyraldehyde, crotonaldehyde, hexanaldehyde, and benzaldehyde)  and of  the
ketones  (acetone and methylethyIketone) in dilute exhaust is accomplished
by collecting these carbonyl compounds in a hydrochloric acid  (HCl)/2,4
dinitrophenylhydrazine  (DNPH) solution as their 2,4 dinitrophenylhydrazone
derivatives.  The derivatives are removed from the HCl/DNPH absorbing solu-
tion by  filtration and/or extractions with pentane.  The filtered precip-
tate and the pentane extracts are combined and the volatile solvents are
removed.  The remaining extract contains the phenylhydrazone derivatives.
The derivatives are then dissolved  in a quantitative volume of toluene  con-
taining  a knowi amount of anthracene as an internal standard.  This solution
is analyzed by injecting a small volume of the solution into a gas chromat-
ograph equipped with dual flame ionization detectors.  From this analysis
and the  measured volume of exhaust  sampled, the concentration of the
carbonyl compounds in exhaust can be determined.  The analysis flow sche-
matic  for the aldehydes and ketones is shown in Figure 3.  A detailed
description of the procedure follows.

     The aldehydes and ketones are  trapped in solution by bubbling a known
volume of dilute exhaust through two glass impingers connected in series,
with each impinger containing 40 m of a 2N HC1 solution saturated with
DNPH.  The sampling temperature and barometric pressure are recorded during
this bubbling period.  The carbonyl compounds in the exhaust react with the
DNPH to  form slightly soluble or insoluble 2,4 dinitrophenylhydrazone deri-
vatives.  The two impingers together collect 98 percent + of the carbonyls
that are present in the exhaust.  The impingers are removed from the sampl-
ing cart and are allowed to stand at room temperature for at least one  hour
before proceeding to the filtration and extraction steps.  Figure 4 shows
two impingers containing the HCl/DNPH absorbing solution after being removed
from the sampling cart.

     Under normal operating conditions the contents of the two impingers
are combined and analyzed as one sample.  If either of the two impingers
contain  a precipitate they are first subjected to a filtration step.  If
no percipitate is present this filtration step is omitted and the extrac-
tion step, described later in the procedure, is the first step.

     For the filtration step the contents of the two impingers are poured
through  a fritted glass filter into a flask under vacuum (Figure 5).  The
two impingers are rinsed with small portions of deionized water.  This  wash
water is also poured through the fritted glass filter.  The precipitate in
the filter is then washed with a few m of deionized water.  The  fritted
filter is then removed from the flask containing the 80 m& of absorbing
reagent  and the water washings.  The flask is then set aside for the ex-
traction step.  The fritted glass filter containing the precipitate is
connected to a dry flask.  The two  impingers that had previously contained
the filtered precipitate are then each washed with small portions of
methylene chloride.  The methylene  chloride dissolves any solid  residue
which was not removed by the water  wash.  These methylene chloride washings
are poured into the fritted glass filter containing the precipitate.  After
                                  A-13

-------
          CVS
   glass  impingers
 derivative  filtered
 and extracted with
pentane  from absorber
filtered ppt combined
with pentane extract
 and solvent removed
extract dissolved in
 toluene containing
  anthracene as an
  internal
   sample analyzed
  in gas chromatograph
      with FID
    A/D converter
      recorder
Hewlett-Packard 3354
   Computer System
Figure 3.  Aldehyde and Ketone analysis flow schematic.
                         A-14

-------
  Figure 4.  Impingers containing HC1/DNPH
             absorbing solution.
Figure 5.  Filtration of absorbing solution.
                   A-15

-------
the precipitate has been dissolved by the methylene chloride, a vacuum is
applied to the flask and the methylene chloride solution is pulled through
the filter into the flask.  Another small amount of methylene chloride is
poured through the filter into the flask to wash the filter.  The methylene
chloride solution is now saved until the extraction step is complete.

     The extraction step is carried out as follows.  The contents of the
two impingers (if no precipitate is present) are transferred to a 250 mSt
separatory funnel.  The impingers are each washed with small portions of
deionized water which is also added to the separatory funnel.  If a pre-
cipitate was found in the impingers the contents of the flask containing
the filtered absorbing reagent and the water washings from the filtration
step are transferred quantitatively to a 250 mi separatory funnel.  The
flask is washed with a small portion of water, and this water is added to
the separatory funnel.  Forty mi of pentane is now added to the separatory
funnel containing the 80 mi of absorbing reagent and water washings.  The
funnel is stoppered and shaken for five minutes in an automatic shaker,
Figure 6.  The shaker is stopped and the funnel is vented.  After the two
phases are allowed to separate, the lower phase is collected in a second
separatory funnel.  The remaining phase is transferred to a third 250 mi
separatory funnel.  A second 40 mi portion of pentane is added to the al-
ready once extracted absorbing solution.  The funnel is again stoppered,
shaken for 5 minutes and vented.  After the phases have separated the
lower phase is again collected in another separatory funnel.  The upper
or pentane layer is combined with the pentane layer from the first extrac-
tion.  A third 40 mi, portion of pentane is added to the twice extracted
absorbing solution and the extraction process repeated.  After the third
extraction the lower layer is discarded and the pentane layer is combined
with the pentane layers from the first two extractions.  Any absorbing
solution which might have been accidently transferred with the pentane
layers is drained off.  Deionized water (25-50 mil) and sodium bicarbonate
(1/4-1/2 gram) is added to the 250 mi separatory funnel containing the 120
mi of pentane extract.  The funnel is stoppered and manually shaken for
30 seconds.  The phases are allowed to separate and the lower water phase
is drained off.  Another 25 mi of deionized water is added and the shaking
is repeated.  After the phases have separated, the water is drained off
insuring that all traces of water are removed.  The contents of the funnel
are then combined with the methylene chloride solution which was saved from
the filtration step.

     The flask containing the methylene chloride solution and the pentane
extracts is then placed in a vacuum oven, Figure 7, operating at 50-60C
and 65" water vacuum until the pentane and methylene chloride have been
removed.  At this time only the dried phenylhydrazone derivatives remain.

     Each time a series of samples are collected a blank containing 80 mi
of HC1/DNPH solution is extracted and dried in the same manner as the
samples.  This accounts for any aldehydes or interfering compounds which
might be found in the reagents used for extraction.

     Two mi of toluene which contain  a quantitative amount of anthracene
C^O.05 mg/m toluene) as an internal standard is pipetted into the flask
                                    A-16

-------
Figure 6.  Automatic shaker.
  Figure 7.  Vacuum oven.
           A-17

-------
containing the dried phenylhydrazone derivatives.  The flask is then placed
in a sonic bath until all of the residue is dissolved.  After the precipi-
tate has dissolved, the solution is transferred to a 1/2 dram vial.   (See
Figure 8.)  At this point the derivative is ready for injection into the
gas chromatograph system.

     The gas chromatograph system used to analyze the toluene solution
containing the phenylhydrazone derivatives is shown in Figure 9.  The sys-
tem consists of a Varian 1700 GC, an  A/D converter, and a recorder.  The
GC is equipped with dual columns and dual flame ionization detectors with
a single differential amplifier.  The columns consist of 24 * 1/8 inch O.D.
stainless steel tubing packed with 6.7 percent Dexsil (polycarboranesiloxane)
300 GC on DMCS treated and acid  washed, 60/80 mesh Chromosorb G.  The
carrier gas is helium which flo?s through the columns at a rate of 40 mVmin.
The optimum hydrogen and air flow rates are 500 m/min and 35 mfi,/nan re-
spectively.  The column temperature, after injection of the sample, is pro-
grammed from 120C to 300C at 8 a minute.  In a chromatogram of a standard
sample (Figure 10) containing anthracene and the phenylhydrazone derivatives
of formaldehyde, acetaldehyde, acetone, iso-butyraldehyde, methylethyl-
ketone, crotonaldehyde, hexanaldehyde, and benzaldehyde, the first peak
eluted is toluene followed by anthracene, and then the derivatives of for-
maldehyde, acetaldehyde, acetone, iso-butyraldehyde, methylethyIketone,
crotonaldehyde, hexanaldehyde and benyaldehyde.  The methylethyIketone
derivative is added to the list of derivatives in order to name an unknown
peak found in some of the exhaust samples.  Data obtained from the five
repetitive injections of the standard derivatives in toluene showed a max-
imum standard deviation of 4.56 percent for benzaldehyde and a minimum
standard deviation of 0.87 percent for formaldehyde.  The computer print-
out of the standard, Figure 10, is shown in Figure 11.  This printout gives
the retention time, area, and the name of each peak.  The printout also
gives the concentration of each of the derivatives in mg/m.  This con-
centration is calculated by the computer from response factors which are
determined daily.  Each day a standard containing known amounts of the de-
rivatives and anthracene is injected into the GC.  From the anthracene and
derivative areas the computer calculates a response factor F.  These F
factors are used in all subsequent runs during the day to determine the
concentration of the derivatives.  This response is calculated from the
following equation:

            Response Factor (F) =  Anthracene Area x mg/m& Derivative
               c                   Derivative Area   mg/m Anthracene

Typical response factors for each of the derivatives are listed below:

                       FACTOR        NAME
                       1.0000        ANTHRACENE
                       3.1043        FORMALDEHYDE
                       2.7736        ACETALDEHYDE
                       2.2366        ACETONE
                       2.4160        ISO-BUTYRALDEHYDE
                       2.3332        METHYLETHYLKETONE
                       3.4174        CROTONALDEHYDE
                                 A-18

-------
           Figure 8.   1/2 dram vials.
Figure 9.  Aldehyde and ketone analytical system.
                     A-19

-------
                                                	I o	
                                          1. Injection
                                           2. Toluene
                                           3. Anthracene
                                           4. Formaldehyde
                                        -_;  5. Acetaldehyde
                                        7_I  6. Acetone
                                        ~  7. Isobutyraldehyde
                                           8. Methylethylketone  ^p
                                           9. Crotonaldehyde
                                         -  10. Hexanaldehyde
                                           11. Benzaldehyde
r-^r^fr-
                 i
                                                    -is
Figure 10.   Chromatogram of standard.
             A-20

-------
REPORT:     i4.il   CHANNEL:  11

SAMPLE:  RCI            IMJECTED AT   11:18:27  JM  .*!AR

i STD  METHOD: DMPHI i
ACTUAL  RUM TI^E:   33.008  4HUTES

1 STD-RAT I 3:     . 353*R MG/1L     STD-A^l:

ENDED NJJ7 J.M  BL
                                                  0533
    KT
             AREA
1L
7. 26
9. 81
1 . 71
2. 64
3.28
3. 73
4. 69
6.38
7.08
9.08
25. 04
JTAL AREA =
9638
1 1 1 59
1 3355
1 7898
1 6448
1 6469
1 1 1 67
1 5988
74
1 0525
187
BB
BB
8V
vv
vv
v/v
\J\J
vv
VB
BB
BB

. 1 90
.202
.21 1
.210
.207
.208
.206
3. 8E- 4
.21 5
9. 7E- 4
122909
                                  &A.
-------
                       2.3428       HEXANALDEHYDE
                       2.9329       BENZALDEHYPE
When the response factor is known a concentration in mg/m for each of the
derivatives can be found.  This concentration, along with the volume of
sampled exhaust is then used to calculate the concentration of the carbonyl
compounds in exhaust.  Figures 12 and 13 show a typical sample chromatogram
and accompanying printout respectively.

 CALCULATIONS

      This procedure has been developed to provide the user with the concen
 trations of the aldehydes  (formaldehyde, acetaldehyde, isobutyraldehyde,
 crotonaldehyde, hexanaldehyde , and benzaldehyde) and ketones  (acetone and
 methylethylketone) in exhaust.  The results will be expressed in Pg/m3 of
 exhaust and ppm for each carbonyl compound.  The equations for determing
 the concentrations in yg/m3 and ppm are derived in the following manner.

      The first step is to correct the volume of exhaust sampled to a stand
 ard temperature, 68 F and pressure, 29.92" Hg, by use of the equation

                        P    v V      P       V
                         exp x  exp _  corr x  corr
                            T       ~      T
                             exp            corr

           vexp  = experimental volume of gas sampled in ft3
           vcorr = volume of gas sampled in ft3 corrected to 68 F and
                   29.92" Hg
           pexp  = experimental barometric pressure
           pcorr = 29.92" Hg
           Texp  = experimental temperature in F + 460
           Tcorr = 68F + 460 = 528R

      Solving for VCOrr gives:
                            P    ("Hg)x v     (ft3) x 528R
                    V     _  exp _ _ _ exp _
                     Crr ~     T    (R)   29.92" Hg
                                 exp

      The next step converts the volume from cubic feet to cubic meters by
 use of the conversion factor 1 cubic meter is equal to 35.31 cubic feet.

                            P    ("Hg)  x V     (ft3) x 528
              v    / 3^  _    exp    ^  x  exp _
               C0rrlm '
                            T    x 29.92" Hg x 35.31
                             exp
                                                                  (Equation 1)
      The next step converts the mg/m of derivative determined by the
 computer to mg of carbonyl collected in the two impingers.  To obtain mg
 of derivative, the concentration  (from the computer printout) in mg/m is
 multiplied by the volume of toluene used to dissolve the sclid extract.
                                 A-22

-------
                                                               ,	I	
  1. Injection
  2. Toluene
  3. Anthracene
  4. Formaldehyde
  5. Acetaldehyde
  6. Isobutyraldehyde
  7. Methylethylketone
  8. Crotonaldehyde
  9. Hexanaldehyde
 10. Benzaldehyde
24
22
20
                   r     i
18
                         16
                         14
                         12
                                           10
                                            8     6
                       Figure 12.  Sample chromatogram.
                                 A-23

-------
Ktr'Jrtl:     20      CHANNEL:  11

SAMPLE:  HCI             INJECTED AT   15:41:05 JM  MAR   1*  1978

I S1U METHJD: 1>MPH1 1


ACTUAL ?"i_)Nl  IM:   3'.1. 31 7 -I I 'JUTES

1 SI U-KA n J:     . 3ba*rt  MG/*1L     SID-AIT:      .0500     SAMP-AIT:      1.3030


    HI        AHEA         MG/ML          NJAMtL




>
tt>



t
,


7. 1 5
7. 95
^.43
1 . 88
^83
3. 78
4. 85
5. 95
6. 77
9. 2"!
itf.fj
?3. 52
? 5. ? 3
35. 48
*435
8877
575
463
1 594
2630
1 46
675
648
1 912
21 7
1 3
84
BV
VB
BB
BV
VV
VV
VV
VV
VV
VB
BV
VV
VB
!JB
.003
. 1 86
.010
.007
.022
.053
.002
.004
.012
.01 1
. 001
7. 6- 5
4. 9E- 4
                                    #F JRMAL DEHYDE
                                    #ACETALDHYDE
                                    #ISJ-BUTYRALDEHYl)E
                                    #CHJ T J.MAL DEHYDE
                                    #H.XA\IAL DEHYDE

                                    #BEMi ^L DEHYDE
 I J'lAL A 
-------
               mg derivative = Cone     (mg/m) x VolTol

     To find mg of carbonyl compound per sample the mg of derivative are
multiplied by the ratio of the molecular weight of the carbonyl derivative
over the molecular weight of its phenylhydrazone derivative.

                                 ,          v  mol. wt. carbonyl
               mg carbonyl = mg derivative x  mol. wt. deriva[ive
                  = Cone     (mg/m) x vol  ,  (mfc) x mol. wt. carbonyl
                        Der   3          Tol        moi. wt. derivative

     To obtain the number of yg of carbonyl compound the mg of carbonyl are
multiplied by the conversion factor, 1000 yg/mg
                                            .    Mol. Wt. carbonyl
    yg carbonyl = ConcDer (mg/mfl x VolTol(mJ6) x MQ;U wt_ derivative
                  x 1000 yg/mg
                                                                (Equation 2)
     me concentration of the carbonyl compound in exhaust can now be found
in yg/m3 by dividing equation 2 by equation 1.

                       Cone     (mg/m) x Vol     (m) x mol. wt. carbonyl
     yg carbonyl/m3 =       -   -           v       3    52go
                                  exp          exp

                           1000 yg/mg XT    (R) x 29.2?" Hg x 35.31 ft3/m3
                        x  _ exP _ . _
                                      mol. wt. derivative
                                                                (Equation 3)


     To find the concentration of each carbonyl compound in ppm, the den-
sities of carbonyls are needed.  At 29.92" Hg and 32F, one mole of gas
occupies 22.4 liters.  This volume is corrected to 68F from the equation.

                                 V   V1
                            Vx = 22.4
                            Tx = 32F +460 = 492R
                            V  = volume at 68 F
                            T  = 68F + 460 = 528R
     Solving for V gives:
               V1 x T   22.4 x 528
           V = - = - = 24.04
                 T         492
                                    A-25

-------
Since one mole of gas occupies  22.045-  at  68F,  the  denisty can be found in
g/ by dividing the molecular weight in g/mole  by 24.04  Vmole

            ,    .  ..   mol. wt.  (g/mole)
           den  (g/&) = - . n.n.  : - -
                y/          24.04Vmole

The density in yg/m can be found by converting g to  yg  and yg and  to
mi as follows:

         d^n ua/mt - mo1' wt. g/mole   1  x  ip6  Vrg/g   mol.  wt. x  IQQQ
         den yg/mfc -- 24.04 Vmole     1  x  103  m/   - 24704 -

                                                                (Equation 4)

To obtain the concentration of  each carbonyl in ppm,  the concentration in
yg/m3 is divided by the density in yg/m
                          ppm = yg/m   T yg/m =  -r
                                                mj

Using Equations 3 and 4 gives the ppm  concentration  in  the  form of  the
raw data.
           CnCDer  (m
-------
                     HP-65 Program Form
Title.
                                                           ace.
                                                                 .of.
  SWtTCH TO W.PRGM PRESS fi PflGM TO CLEAR MEMORV
KEY
ENTRY
LBL
A
9

o
0
0
5
*
KR/S
X
ST01
R/S
4
6
0
+
RCL1
a x v
X***
q 1/X
R/S
X
ST02
R/S
RCL2
X
0

-0 1
4
3
X
R/S
RCL 2
X
0

1
-c 9
6
. X
R/S
RCL 2
X
0

2
4
- 4
CODE
SHOWN
23
11

83




71
84
71
3301
84



61
3401
3507
31
3504
84
71
3302
34
3402
,.,.?! ,.

33


F
71
94
3402
71

83



71
34
3402
71

83



COMMENTS

Input sample vol. , ft^







Inout Barometer, "Hq


Input sample Temo F








Input Vol. Toluene, ml


In ma/mj.








Out ug/m^; In mg/ml








Out '^Q/m3: Tn ma /ml







KEY
ENTRY
X
R/S
RCL2
X
0

2
a
6
60 X
R/S
RCL2
X
0

2
8
6
X
re R/S
RCL2
X
0
.
2
3
0
X
R/S
S.RCL2
X
0
,
3
e;
Q
X
R/S
RCL 2
30 X
0

3
7
1
X
R/S
RTN


CODE
SHOWN
71
34
3402
71

83



71
84
3402
71

83



71
84
3402
71

83



71
84
3402
71

83



71
84
3402
71

33



71
84
24


COMMENTS

Out yg/m3; In mg/ml








[Out ug/raJ; In mg/ml








Out Ug/m3; in mg/ml








Out u
-------
               HP-65 User Instructions
Programmer

/'_
0_



-I 	 L


] i
_i  i mi \


/
U 	 L 1



_L



i m
J
1
STEP
01
02
3
A
1
2
3
4
5



7

S

9

10

11

12



INSTRUCTIONS
Switch to on; switch to run
Feed card in from right to left
Initialize
Set decimal place
Input - sample volume, ft3
Input - barometric pressure, "Kg
Input - Sample Temperature, F
Input - Volume Tolune, ml
Input - Cone. Formaldehyde Der, rag/ml
Output - Cone. Formaldehyde Ug/m3
Inout - Cone. Acetaldehvde Der. ma/ml
Output - Cone. Acetaldehyde Ug/m3
Input - Cone. Acetone Der, mg/ml
Output - Cone. Acetone, Ug/m3
Input - Cone. Isobutyraldehyde Der, mg/ml
Output - Cone. Isobutyraldehyde, Ug/m3
Input - Cone, methylethylketone Der, mg/ml
Output - Cone, methylethylketone, Ug/m3
Input - Cone. Crotonaldehyde Der, mg/ml
Output - Cone. Crotonaldehyde, Ug/m3
Input - Cone. Hexanaldehyde Der, mg/ml
Output - Cone . Hexanaldehvde , jj g/m3
Input - Cone. Benzaldehvde Der, mo /ml
Output - Cone . Benzaledhvde Ua/m3


INPUT
DATA/UNITS


























KEYS
II 'I
II 1
f II REG 1
DSP || 2 I
A || I
R/s II I
R/S J|
R/s II
R/s II
II
R/S II 1
II
R/S II 1
II 1
R/S II
II
R/S II
II
R/S II 1
II 1
 K II 1
H
R/S II
H
RTN II 1
f II 1
OUTPUT
DATA/UNITS

























(cont'd.)
Figure 14 {Cont'd).   Aldehyde and Ketone concentrations  in yg/m.
                         A-28

-------
   HP-65 User Instructions


/ ]
b _i  i  i  !  dsl


/
n  i  1_



JL
DatP

J

STEP
01
02
?
4
1

2

3

4

5

6

7

3







INSTRUCTIONS
Switch to on; switch to run
Feed card in from right to left
Initialize
Set decimal place
Input-cone Formaldehyde, yg/m3
Ouput-conc Formaldehyde, ppm
Input-Cone Acetaldehyde , Ug/m
Output-Cone Acetaldehyde, ppm
Input-Cone Acetone, ug/m3
Output-Cone Acetone, ppm
Input-Cone Isobutyraldehyde, Uq/m3
Output-Cone Isobutyraldehyde, ppm
Inout-Conc Methvlethvlketone, ucr/m3
Outout-Conc Methylethvlketone. oom
Input-Cone Crotonaldehyde . ua/m-'
Output-Cone Crotonaldehyde, ppm
Input-Cone Hexanaldehyde , ug/m3
Output-Cone Hexanaldehyde, ppm
Input-Cone Benzaldehyde , yg/mj
Output-Cone Benzaldehyde , ppm






INPUT
DATA/UNITS


























KEYS
1 II
1 II
f || REG
PDSP || 2 ]
1 , II
1 II
r;,c ii i
II
1 . II 1
i ir i
1 R/S II 1
i ii
1 R/s II 1
i ir i
[ R/s 11
r i! i
. ii
i ii i
.* ii
i ii
| RTN ||
1 f II 1
REG ]f
CLX II
II
II
OUTPUT
DATA/ UNITS


























Figure 15.  Aldehyde and Ketone concentrations in ppm.
           A-29

-------
                          i

KEY CODE rnMMFWTc; 1
ENTRY SHOWN COMMENTS j
L3L ! 23
A 11 ! Ir. cone ug/n-*
1
2
4
9
T 31
R'S 34 j Out cone pom
In cone ug/m^
- 1
B
3
2
f 31
R/S 34 Out cone ppm
In cone UQ/m-5
2 1
., !
1
.'6 1
T ' gi
R/C 94 Out cc-ic ppra
In eor.c ^c/n^
3 i
n
0
0
r , 31
R/S 54 i Out cone ppin
In 7onc ua/n-'
: !
0 i i
-1 '
0 i
:- 31
f/S 94 Out cone ppm
j In cone _ a/n\J
2 I
9
. i l
6 1 ;
7 ' 31
K/J? -i4 .""Mr -^nc  r.m
In core jq/m-1
4
1
6 !
6 !
* ' 81
- P/S ; 34 ; 3at cone c^n


KEY
ENTRY

^
4
1
5

R/S
r.TN

-C



















l^" "





I














'C HE^OKO f

CODE
SHOWN





31
24
24












































COMMENTS
Ii: cone ja/nj
1




Cu- --one ppm
|











!
I





i


'
|





1




1
1

i
i
i
i


"4CV * C CiSC AITH SA'TCH :ET - ' N P = OM

REGISTERS
Ri


R?



i

R4

1
Rs

!
Re 1
i
i
R? i
!
I
Rs


Ro

1
! LABELS 
A :
B
\ c
D i
E
O

2
3 '
4
5
6
^
a
9
1
FUGS
1 ,

2



rigure 15 ConL'd;.  Alaenyae ana Ketone concentrations in ppm.
                         A-30

-------
Sample Calculation

     Assxime exhaust samples were collected in glass impingers for each por-
tion of a three bag 1975 FTP.  Raw data for these tests is presented in
Figure IS.  Calc-lr.Lions were performed using the HP-65 programs and manual
calculations.

Manual calculation for driving cycle FTP-1:
                          Cone    (mg/m) x vol    (m&) x mol. wt. carbonyl
     yg/m3 formaldehyde = 	^^_	      x  	^^	
                                   exp          exp

                              1000 yg/mg x T     (R) x 29.92" Hg
                                          528R

                            x 35.31 ft3/m3	
                              mol. wt. derivative

                           0.186 mg/m x 2m x 30.03 g/mole x IQQQ yg/mg
                                  29.80" Hg x 3.196 ft3 x 528R

                            x 535R x 29.92" Hg x 35.31 ft3/m3
                                         201.15 g/mole

                        =  597.5 yg/m3

                           ppm formaldehyde = yg/m  T density yg/m

                                   .    mol. wt. (formaldehyde) x IQOO
                        density yg/m = 	     .	=*	
                           mol. wt. formaldehyde = 30.03 g/mole

                                  30.03 g/mole x IQQQ _      1Irr/mp
                        density = 	    041,	        yg/mJ6

          ppm = 597.5 yg/m3 T 1249 yg/m = 0.478 m/m3 = 0.478 ppm

The calculations for acetaldehyde, acetone, isobutyraldehyde, methylethy-
ketone, crotonaldehyde, hexanaldehyde, and benzaldehyde are carried out in
the same manner by substituting the appropriate derivative concentrations
and molecular weights into the above formulas.  These calculations give the
following concentrations:

     acetaldehyde, 561 yg/m3 and 0.306 ppm
     acetone, 663 yg/m3 and 0.274 ppm
     isobutyraldehyde, 141 yg/m3 and 0.047 ppm
     methylethylketone, 630 yg/m3 and 0.210 ppm
     crotonaldehyde, 541 yg/m3 and 0.186 ppm
     hexanaldehyde, 250 yg/m3 and 0.060 ppm
                                  A-31

-------
SWRI PROJECT NO.	



FUEL:	CVS NO.	



SAMPLE COLLECTION BY:_



GENERAL COMMENTS:	
                       TEST NO.
TUNNEL SIZE:
                JTEST DATE:_



                   DRIVER:
     CHEMICAL ANALYSIS BY:
                                                            VEHICLE:
                                   MILES:
                               CALCULATIONS BY:
Test No.
Driving Cycle
Volume, Ft 3
B.P., "Hg
Temp. F
Vol. Toluene ml
Formaldehyde Der Cone mg/ml
Formaldehyde Cone Ug/m
Formaldehyde Cone ppm
Acetaldehyde Der Cone mg/ml
Acetaldehyde Cone yg/n\3
Acetaldehvde Cone DDIH
Acetone Der Cone mg/ml
Acetone Cone pg/m3
Acetone Cone ppm
I-Bu Aldehyde Der Cone mg/ml
I-Bu Aldehyde Cone ug/n>3
I-Bu Aldehyde Cone opm
MeEt Ketone Der Cone mg/ml
MeEt Kfitone Cone ug/m3
MeEt Ketone Cone ppm
Cro-Aldehyde Der Cone mg/ml
Cro-Aldehvde Cone pg/m3
Cro-Aldehyde Cone ppm
Hex-Aldehyde Der Cone mg/ml
Hex-Aldehyde Cone pg/m3
Hex-Aldehyde Cone ppm
Benzaldehyde Der Cone mg/ml
Benzaldehyde Cone Ug/m3
Benzaldehyde Cone ppm
FTP-1
3.196
29.80
75 .
2
0.186
598
0.479
0.127
559
0.305
0.121
663
0.274
0.022
141
0.047
0.098
630
0.210
0.086
541
0.186
0.031
250
0.060
0.093
775
0.176
FTP-2
1,625
30.02
80
2
0.105
665
0.532
0.092
798
0.436
0.098
1060
0.439
0.011
139
0.046
0.084
1060
0.353
0.074
917
0.314
0.018
286
0.069
0.081
1330
0.301
FTP- 3
2.010
29.02
96
2
0.201
1100
0.881
0.157
1170
0.639
0.161
1500
0.621
0.028
305
0.102
0.097
1060
0.353
0.076
811
0.278
0.030
411
0.099
0.097
1370
0.310
SET-7
3.730
29.25
85
2
0.312
891
0.713
0.282
1100
0.600
0.285
1390
0.575
0.023
131
0.044
0.198
1130
0.377
0.105
587
0.201
0.027
194
0.047
0.121
897
0.203
HFET
8.241
29.95
83
2
0.732
921
0.737
0.612
1060
0.579
0.595
1280
0.530
0.051
128
0.043
0.252
634
0.211
0.286
705
0.242
0.078
246
0.059
0.232
757
0.171
NYCC
1.070
29.50
89
2
0.142
1410
1.130
0.102
1390
0.759
0.105
1780
0.737
0.009
179
0.060
0.075
1490
0.497
0.072
1400
0.480
0.011
275
0.066
0.081
2090
0.473
              Figure  16.   Aldehyde  Collection Sheet.
                                       A-32

-------
      Benzaldehyde, 775  g/m3 and 0.176 ppm.

 Note:  The values used in these calculations are picked from a range of
 temperatures, derivative concentrations, etc. to validate the calculations
 and may not be representative of expected raw data.  The calculations are
 presented to confirm the manual and HP-65 calculations give the  same re-
 sults.  This was confirmed for six sets of calculations.

 REFERENCES

      This procedure is taken from the procedure:  "Oxygenated Compounds in
 Automobile Exhaust-Gas Chromatograph Procedure" by Fred Stump, ESRL,
 Environmental Protection Agency, Research Triangle Park, North Carolina.
THIS PROCEDURE IS REPRINTED FROM  EPA  REPORT  EPA 600/2-79-017,
"ANALYTICAL PROCEDURES FOR CHARACTERIZING UNREGULATED POLLUTANT
EMISSIONS FROM MOTOR VEHICLES."   (Reference  3)
                                  A-33

-------
                             APPENDIX A-5

                         MEASUREMENT OF METHANOL

     The measurement of methanol in exhaust is accomplished by bubbling
the exhaust through glass impingers containing deionized water.  The
exhaust sample is collected continuously during the test cycle.  For
analysis, a portion of the aqueous solution is injected into a gas
chromatograph equipped with a flame ionization detector (FID).  External
methanol standards in deionized water are used to quantify the results.
Detection limits for this procedure are on the order of 0.06 ppm in
dilute exhaust.

SAMPLING SYSTEM

     Two glass impingers in series, with each containing 25 mfc of deion-
ized water are used to collect exhaust samples for the analysis of methanol.
A flow schematic of the sample collection system is shown in Figure 1.
The two glass impingers collect 99 percent of the methanol in exhaust.
The temperature of the impinger is maintained at 0-5C by an ice water
bath, and the flow rate through the impinger is maintained at 4&/minute
by the sample pump.  A dry gas meter is used to determine the total flow
through the impinger during a given sampling period.  The temperature
of the gas stream is monitored by a thermocouple immediately prior to
the dry gas meter.  A drier is included in the system to prevent conden-
sation in the pump, flowmeter, dry gas meter, etc.  The flowmeter in the
system allows continuous monitoring of the sample flow to insure proper
flow rates during the sampling.  Several views of the sampling system
are shown in Figure 2.

ANALYTICAL PROCEDURE

     The analysis of methanol is accomplished by collecting methanol
in deionized water and analyzing the sample with a gas chromatograph
equipped with an FID.  The analysis flow schematic for methanol is shown
in Figure 3.  A detailed description of the procedure follows.

     For the analysis of methanol, dilute exhaust is bubbled through
two glass impingers each containing 25 m& of deionized water.  Upon
completion of each driving cycle, the impinger is removed and the contents
are transferred to a 30 m& polypropylene bottle, and capped.

     A Perkin-Elmer 3920B gas chromatograph equipped with a flame ioniza-
tion  detector is used to analyze the sample.  A 5 y& portion of the
sample is injected into the gas chromatograph  (GC).  The column is a
3' X 1/8" Teflon column containing 120/150 mesh Porapak Q.  The carrier 
gas is helium which flows through the column at a rate of 20 m/minute.
The column temperature is maintained at 100C.  A chromatogram of a
standard sample containing 63 ppm methanol is shown in Figure 4.  To
                                A-34

-------
                                                                          Gas Temperature
                                                                          Digital Readout
u>
in
                      On-Off
                   Solenoid Valve
         Sample
         Probe
iXh-i
        Dilute
        Exhaust
 Dry
 Gas
Meter

                                                       Ice Bath
                                                  Temperature Readout
                                                                         Gas Volume
                                                                       Digital Readout
                             Figure 1.  Methanol sample collection  flow
                                                  schematic.

-------
             Front View
                                                Digital
                                                Readout
                                                Flowmeter
                                                Regulating
                                                Valve
       Close-up of Upper Front
Figure 2.  Methanol sampling system.
               A-36

-------
                 f J
Solenoid
Impinger
Ice Bath
                       Close-up of Impingers (Side View)
                                                   Pump
              Rear View
         Figure 2 (Cont'd).   Methanol sampling system.
                          A-37

-------
        CVS
       Glass
     Impinger
 Unused Sample
saved as needed
          I
    Sample analysis
in gas chromatograph
     with FID
 A/D Converter
          I
        I
     Recorder
Hewlett-Packard
     3354
Computer System
      Figure 3.   Methanol analysis flow schematic.
                     A-38

-------
                                 I.D. Teflon  Type
                                            Liq. Phase
                                             Support
                                              Carrier
  on  120/150 mesh
                     Rotameter Reading
                          min., Prog to    C at
  held for_
Inlet  150
          /min. Held for
           	min.
                  (other)
               C.  Heated-Glass  Lined"
Detector   200  C  FID
                                              _Type
  Hvd   33   psig	
  Air   57   psig	
  (  )	psig	
Recorder  1   in/min speed
Injection 5    ul indicated
                      	Type (other)
                      . Rotameter Rdg.
                       Rotameter Rdg.
                       Rotameter Rdg.
                      _1	mV.F.S..
                               ul net
                                                cc/min
                                       _ cc/min
                                                cc/min
                                        Sol tec" TVP>
                                              ul Actual
           Retention  time, min.
Figure  4.   Chromatogram of methanol standard
                       A-39

-------

Figure 5.   Methanol Analytical system.

-------
quantify the results, the sample peak area is compared to the peak area
of a standard solution.  Figure 5 shows the analytical system with gas
chromatograph, detector, A/D converter, and recorder.

CALCULATIONS

     The procedure has been developed to provide the user with the concen-
tration of methanol in exhaust.  The results will be expressed in yg/m3
of exhaust and ppm.  The equations for determining the concentrations
in yg/m  and ppm are derived in the following manner.

     The first step is to correct the volume of exhaust sampled to a
standard temperature, 68F, and pressure, 29.92"Hg, by use of the equation


                    P    x V       P     x V
                     exp     exp =  corr	corr
                        T             T
                         exp           corr


     Vexp  = experimental volume of gas sampled in ft
     vcorr = volume of gas sampled in ft3 corrected to 68F and 29.92"Hg
     Pexp  = experimental barometric pressure
     pcorr  29.92"Hg
     Texp  = experimental temperature in F + 460
     Tcorr = 68F + 46 = 528R

     Solving for Vcorr  gives:


                            P    ("Hg) x V    (ft3) x 528R
                    v     =  expv  *'    exp      	
                     corr       T     (R) x 29.92"Hg



     The next step converts the volume from cubic feet to cubic meters by
use of the conversion factor: 1 cubic meter is equal to 35.31 cubic feet.


                                P     ("Hg) x V    (ft3) x 528R
                    v         =  exp    *     exp
                     corr(m3)   Tx 29.92"Hg x 35.31 ft3/m3
                                 exp

                                                                   (Equation 1)


     The next step is to find the concentration of methanol in yg/mH.  Since
the gas chromatograph FID has a linear response in the concentration of concern,
then the following equation holds.


                    Csam (W/mSL}   Cstd
                       A              A _
                        sam            std
                                 A-41

-------
     Csam = concentration of the sample  in yg/m
     Asam = GC peak area of sample in relative  units
     Cstd = concentration of the standard  in yg/md
     Astd = GC peak area of standard in  relative  units

     Solving for Csam gives:


                                 (yg/mJO  x  A
                                   std
     The Csam(yg/mJl) in solution is corrected  for  any necessary dilution by
multiplying by the dilution factor, D.F.
                          = Cstd  (^/m*> * ASam
                                     Astd
     To obtain the total amount in yg of methanol  in  the aqueous  absorbing
solution, the absorbing reagent volume is multiplied  by  the concentration
to give:

     yg sample = Csam  (yg/mJl) x Abs. Vol.  (mi)
                 c +.j  (yg/mJl) x A    x D.F. x Abs. Vol.
                  s L.Q.
                                 Astd
                                                                    (Equation 2)
     To obtain yg sample/m3, Equation 2 is divided by  Equation 1 to give:
                  C .  ,  (yg/mfc) x A    x D.F. x Abs. Vol.  (m)
              3    SuQ            S3.IB
                = 	r1T5	("Hg) x 528	
                          std    exp    '
                   gx
                       x 29.92"Hg x 35.31  (ft3/m3)
                           V     (ftj)
                            exp
                                                                    (Equation 3)


                                  A-42

-------
     To find the concentration of methanol  in ppm,  the  density of the
methanol is needed.  At 29.92"Hg and  32F,  one mole of  gas occupies
22.4 liters.  This volume is corrected  to 68F from the equation

                       _V = Vj_
                        T   TI

     Vi = 22.4&
     TI = 32F + 460 = 492R
     V  = volume at 68F
     T  = 68F + 460 = 528R

     Solving for V gives:
           V -       -      '42     -  24.04.


Since one mole of gas occupies 22.04& at 68F, the density  can be found in
    by dividing the molecular weight in g/mole by 22.04  A/mole
                       mol. wt. g/mole
                       24.04
The density in yg/iafc can be found by converting g to yg and  H  to  mH  as
follows:
       den yg/mJl = mol. wt. g/mole   1 x IQ^yig/g _ mol. wt. x  1000
                   24.04 Vmole    X 1 x lO^mil/il ~        24.04
                                                                    (Equation  4)
To obtain the concentration of methanol in ppm, the concentration  in
is divided by the density in yg/m&


       ppm = yg/m3 v yg/mJl = 7	
                              j
                                    A-43

-------
Using Equations 3 and 4 gives the ppm concentration in the  form  of  the  raw
data.
                24.04U) x C   ,  (ug/mfc) x A    x D.F. x Abs. Vol.  (mil)
              _ 	std	sam
          Ppm ~     Mol. Wt.  (g/mole) x 1000 x A ., X P     ("Hg)
                                                std    exp

                           T    (R) x 29.92"Hg x 35.31 ft3/m3
                         x  e 	
                                 528R x V(ftj)
                                          exp
                                                                    (Equation 5)
At this point, the concentration can be expressed  in ug/m3  (Equation 3)  and
ppm  (Equation 5) at 68F and 29.92"Hg  from the raw data.

Hewlett-Packard Calculations

     In order to insure maximum turnaround in a minimum time period, a
Hewlett-Packard 67 program was developed  to  calculate  the methanol concen-
trations in  yg/m3 and ppm from the  raw data.  This program  is presented in
Figure 6.

Sample Calculation

     Assume  exhaust samples were collected in glass impingers for each
portion of a three bag 1975 FTP.  Raw  data for these tests  are presented
in Figure 7.  Calculations were performed using the HP 67 program and
manual calculations.

Manual calculations for driving cycle  FTP-1

     For Bubbler #1
                      C   , (yg/mJl) x A     x D.F. x  Abs. Vol. (mZ)
         M/B3CH3OH - ^	jHS	    	
                                 std    exp

                      T    x 29.92"Hg  x 35.31 ft3/m3
                       exp	
                    X      528R x  V(ftj)
                                    exp


                    =  (7.9 yg/m) x 1000  x 1 x  25
                            1500 x  29.80"Hg

                                 

                    x  (460 + 75) x  29.92"Hg  x 35.31  ft3/m_3
                                528R x 3.196 ft-5

                    = 1480 Ug/n3

                                  A-44

-------
       Figure 6.  KP-67
User Instructions
STEP
0
02
03
1
2
3
4
5
6
7
8
9
10
11
12
13
14
15
16




















INSTRUCTIONS
Switch to on; switch to run
Feed side 1 of card in from right to left
Set decimal place
Input Sample Volume
Input Barometric Pressure
Input Sample Temperature
Input Absorbing Reagent Volume
Input Dilution Factor, Bubbler #1
Input Standard Concentration, Bubbler #1
Input Standard Area, Bubbler #1
Input Sample Area, Bubbler #1
Output Sample Cone. , Bubbler #1
Input Dilution Factor, Bubbler #2
Input Standard Cone., Bubbler #2
Input Standard Area, Bubbler #2
Input Sample Area, Bubbler #2
Output Sample Cone, Bubbler #2
Output Sample Cone., Bubbler # 1 & #2
Output Sample Cone.




















INPUT
DATA/UNITS



ft3
"Hg
OF
mjj,

yg/m&
counts
counts


Uq/mA
counts
counts























KEYS
L 	 1
[R/sJ
TR/S 1
1 Sci 1
[R/jij 1 	 1
[R/sJ
i R/S 1
GB/S_]
LR/S 1
Lfi/sJ
1 R/sJ
1 R/S 1
LIZ]
L_"J
L .1
1 	 J
H
L_J
rn
r~ J
r n
cm
r i
L. 1
L_.J
L J
r ;j
L J
i
i
L""J
LIZ)
1 1
i ~j r ~ i
J__
r _
[ 	 ]
[ j
i i
LZ:I
i
\ -
r i
i J
L Z_l
L -J
I
1 1
r J
OUTPUT
DATA/UNITS











uq/mfc




yg/m&
yg/m
ppm




















          A-45

-------
STEP









010









020









030









040









050






KEY ENTRY

2

R/S
X
STO 1
R/S
4
6
0
+
RCL 1

R/S
X
STO ?
RCT, ?
R/S
y
R/S
X
R/S
T
R/S
X
STO 3
R/S
ROT. ?
Y
R/S
Y
R/S
i
R/S
X
R/S
RCL 3
+
R/S
1
3
-?
3

R/S
h RTN










Figure 6 (Cont'd). HP- 67 Program Form
KEY CODE COMMENTS STEP KEY ENTRY KEY CODE COMMENTS
31 25 11
02
81
84
71
33 01
84
04
06
nn
fil
34 01
81
84
71
33 02
34 02
84
71
84
71
fij
nl
fld
71
33 m
4
14 02
71
84
71
R4
HI
4
71
84
34 03
61
Rd
01
03
03
03
81
84
35 22










In Sample Vol . , ft3


In Barometric Press-
ure, "Hg
In Sample Temp, F
In Sol. Vol. , mi
In Dilution Factor
[n Std Cone . , ug/mJl
In Std. Area
In Sample Area,
Bubbler #1
Out Sample Cone.
Bubblerfl, yg/m3
In Dilution Factor
Cn Std Cone., yg/mJl
Input Std . Area
En Sample Area,
Bubbler #2
Out Sam. Cone,
Bubbler #2, yg/m3
Out Cone . , yg/m
Output ppm Methanol





060









070









080









090









100









10





























































































































REGISTERS
01234
SO S1 S2 S3 S4
A E
> C
567
S5 S6 S7
D E
8 9
S8 89
E I
A-46

-------
STEP  KEY ENTRY   KEY CODE
Figure 6  (Cont'd)



    COMMENTS
HP-67 Program Form



STEP  KEY ENTRY   KEY CODE
                                                                                   COMMENTS
001








010









020









030









040









050






f LBL A
2
i
R/S
X '
STO 1
R/S
4
6
0
+
RCL 1

R/S
X
STO 2
RCL 2
R/S
X
R/S
X
R/S

R/S
X
STO 3
R/S
RCL 2
X
R/S
X
R/S
.
R/S
X
R/S
RCL 3
+
R/S
1
3
3
3
j.
R/S
h RTN










31 25 11
02
81
84
71
33 01
84
04

nn
61
u m

84
71
33 02
34 02
84
71
84
71
84
81
84
71
33 03
84
34 02
71
84
71
84
81
84
71
84
34 03
61
Rd
01
m
m
m
sn
84
35 22










In Sample Vol., ft3
In Barometric Press-
ure, "Hg
In Sample Temp. , F



In Sol. Vol., mi



In Dilution Factor

In Std Cone . , yg/mfc

In Std. Area

In Sample Area,
Bubbler #1
Out Sample Cone. -
Bubbler #1, yg/m3
In Dilution Factor
In Std . Cone . , yg/mA
Input Std. Area
In Sample Area,
Bubbler #2
Out Sample cone . , ,
Bubbler #2, yg/nr3

Out Cone . , yg/m



Output ppm Methanol






060









070









080









090









100









110



















































































































REGISTERS
01234
SO S1 S2 S3 S4
A
3 C
56789
S5 S6 S7 SB S9
D
E I
                                             A-47

-------
                                                METHANOL
          SWRI  PROJECT NO.	



          FUEL	CVS NO.



          SAMPLE COLLECTION BY:  _



          GENERAL COMMENTS	
                                     TEST NO.
                                                         TEST DATE:
                                                                               VEHICLE:
     TUNNEL SIZE:
                             DRIVER:
                                                MILES:
CHEMICAL ANALYSIS BY:
                               CALCULATIONS BY:
CO
Test No. 1234
Driving Cycle 	
Volume, Ft3
B.P., "Hg
Temp. F
Absor. Rea. Vol., m
Dilution Factor, Bubbler #1
Std. Cone UgCHiOH/m Bub. #1
Std. Area - Bubbler #1
Sample Area - Bubbler #1
Samel e Cone UgCHiOH/m3 , Bubtl
Dilution Factor, Bubbler #2
Std. Cone ViqCH^OH/mJlBub. #2
Std. Area - Bubbler #2
Sample Area - Bubbler #2
Sample Cone ugCHiOH/m3,Bub#2
Total Cone. ygCH^DH/m3
PPM Methanol
FTP-1
3.196
29.80
75
25
1
7.9
1500
1000
1480
1
0.79
2000
500
55.5
1530
1.15
FTP-1
1.625
30.02
80
25
5
79
5000
1000
43700
2
7.9
1500
300
1750
45500
34.1
FTP- 3
2.010
29.02
96
50
10
790
10000
1000
753000
5
7.9
5000
6000
45200
798000
599
SET- 7
3.730
29.25
85
50
2
7.9
1000
3000
23700
1
0.79
1000
100
39.5
23700
17.8
5
HFET
8.241
29.95
83
75
1
7.9
5000
15000
7820
1
0.79
6000
1000
43.5
7860
5.90
6
NYCC
1.070
29. SO
89
75
1
0.79
1000
3000
6180
1
0.79
5000
15000 _
6180
12400
9.28
                                    Figure 7.   Methanol sample collection sheet

-------
     The concentration in Bubbler #2 is calculated in the same manner
using the appropriate dilution factor, standard concentration, standard
area, and sample area:

     For Bubbler #2:

                  0.79 uq/m& x 500 x 1 x 25
              3 = - ca' -
                        2000 x 29.80


                x (460 + 75) x 29.92"Hg x 35.31 ft3/m3
                         528R x 3.196 ft3

                =55.5 yg/m3
     The concentrations from the two bubblers can be added for a total
concentration :

          Total yg methanol/m3 = cone. (Bubbler #1) + cone. (Bubbler #2)
                               = 1480 yg/m3 +55.5 yg/m3
                               = 1535 yg/m3

     PPM CH3OH = yg/m3 -f density yg/m

                     / o   Mol. Wt.  (CH^OH) x 1000
          density yg/m* = -


          Mol. Wt. CH3OH = 32.04 g/mole


          density = 32.04 x 1000    _,,,    . 
                i   - . - = 1333 yg/mJt
                        24.04

     ppm = 1535 T 1333 yg/m = 1.15 mi/m3 = 1.15 ppm
Note:  The values used in these calculations are picked from a range of
temperatures, standards, dilution factors, etc., to validate the calculations
and may not be representative of expected raw data.  These calculations are
presented to confirm that the manual and HP-67 calculations give the same
results.  This was confirmed on six sets of calculations.
                                   A-49

-------
LIST OF EQUIPMENT AND REAGENTS

     The equipment and reagents for the analysis of the methanol is
divided into two groups.  The first involves the sample acquisition and
the second the instrumental analysis of the sample once it has been obtained.
Manufacturer, stock number and any pertinent descriptive information are
listed.  The preparation of standards is also discussed.

Sampling

 1.  Glass impingers, Ace Glass Products, Catalog #7530-11, plain tapered
     tip stoppers with 18/7 arm joints and 29/42 bottle joints.

 2.  Flowmeter, Brooks Instrument Division, Model 1555, tube size R-2-15-C,
     graduated 0-15, sapphire float, 0-5 i/min range.

 3.  Sample pump, Thomas Model 106 CA18, capable of free flow capacity of
     4
 4.  Dry gas meter, American Singer Corporation, Type AL-120, 60 CFH
     capacity.

 5.  Regulating valve, Nupro 4MG, stainless steel.

 6.  Teflon tubing, United States Plastic Corporation, 1/4" OD x 1/8" ID
     and 5/16" OD x 1/8" ID.

 7.  Teflon solenoid valve, the Fluorocarbon Company, Model DV2-144NCA1.

 8.  Drying tube, Analabs Inc., Catalog #HGC-146, 6" long, 1/4" brass
     fittings.

 9.  Miscellaneous Teflon nuts, ferrules, unions, tees, clamps, connectors,
     etc.

10.  Digital readout for dry gas meter.

11.  Miscellaneous electrical switches, lights, wirings, etc.

12.  Six channel digital thermometer, Analog Devices, Model #2036/J/1.

13.  Iron/Constantan type J single thermocouple with 1/4" OD stainless
     steel metal sheath, Thermo Sensors Corporation.

14.  30 mH polypropylene sample storage bottles, Nalgene Labware, Catalog
     #2006-0001.

15.  Deionized or distilled water.

16.  Class A, 10 mi volumetric pipet.

17.  Class A, 1000 m volumetric flask.

                                 A-50

-------
Instrumental Analysis

 1.  5 yl syringe, Hamilton Co., Reno, Nevada.

 2.  Perkin-Elmer Model 3920 B gas chromatograph equipped with  flame
     ionization detector.

 3.  Soltec Model B-281 1 mv recorder.

 4.  Hewlett-Packard Model 3354 gas chromatograph computer system with
     remote teletype printout.

Preparation of Primary Standards

     The primary standard for the methanol analysis is prepared by diluting
a known volume of methanol with deionized  (or distilled) water.  Standards
less than VDOO ppm are prepared by diluting higher concentration standards
with deionized water.
  THIS PROCEDURE IS REPRINTED FROM EPA REPORT EPA 460/3-82-004,
  "CHARACTERIZATION OF EXHAUST EMISSIONS FROM METHANOL AND
  GASOLINE FUELED AUTOMOBILES." (Reference 5)
                                   A-51

-------
                               APPENDIX A-6

                          MEASUREMENT OF  ETHANOL
     The measurement of ethyl alcohol in exhaust and evaporative emissions
was accomplished by direct bag analysis using a gas chromatograph equipped
with a flame ionization detector.  A limited number of qualification and
validation experiments were conducted to insure the accuracy and reliability
of the procedure.  Contacts were made with key individuals at EPA, Ann Arbor
and Research Triangle Park to coordinate the approach to this analysis with
other participants in the evaporative emissions program.

Analytical System

     The analysis for ethyl alcohol in exhaust and evaporative emissions is
conducted using a gas chromatograph equipped with a flame ionization detector.
The system employs two pneumatically operated electrically controlled Seiscor
valves, one in a gas sampling valve configuration and the other in the back-
flush configuration.  Figure A-l illustrates the flow schematic of the analy-
tical system.

     The system was deisgned for bag analysis and used normal CVS bag samples
for the exhaust emissions.  In the case of the SHED emissions, bag samples
were collected during the first and last minute of the soak.  These bags
were then transported to the gas chromatograph for subsequent analysis.

     The analytical column selected for this separation was a 10' x 1/8" SS
with 15% TCEP on 60/80 Chromosorb P.  The separation of ethyl alcohol from
benzene and toluene was satisfactory and no known interferences were en-
countered.  The gas chromatograph oven was maintained at 50C and the system
was backflushed after the toluene peak.  The total analysis time was 45-60
minutes.  A typical separation of ethyl alcohol and the two closest eluting
compounds is presented in Figure A-2.  The specific GC operating parameters
for this separation is presented in Table A-l.

Control System

     The control of the two Seiscor valves is accomplished by ATC timers
and ASCO electric solenoid valves.  The electrical schematic for the control
of the Seiscor valves using these timers and electric solenoid valves is
shown in Figure A-3.  The flow schematic for the vacuum and pressure lines
to the Seiscor valves are presented in Figure A-4.

Equipment

     This analysis is performed using a gas chromatograph equipped with a
flame ionization detector.  The gas chromatograph, recorder and data ac-
quisition system are major components in the detection system.  A control
console was fabricated to house the mechanical hardware items that are
necessary for the proper operation of the ethyl alcohol analysis system.
The major items that are included in each of these systems is listed ds
follows:
                                  A-52

-------
       Analytical Column
    (10'  x 1/8"  SS  15% TCEP)
      Seiscor Valve
(backflush configuration)
                                                          Perkin-Elmer
                                                             900
                                                        Flame lonization
                                                            Detector
                                 Seiscor Valve
                           (Gas  Sampling Configuration)
                                                                 Carrier
                                                                  Gas
                  TT
          mmmmmmmmwmmmmmmmmmmmmmmmmmm*
Vent
                                             10 ml sample loop
                                              Regulating
                                                Valve
                                Pump
         ft'
         Flowmeter
                                                         Female
                                                       Quick-Connect
             Figure 1.  Ethyl Alcohol Analytical Flow Schematic
                                  A-53

-------
23  22   21   20   19  18   17   16  15   14   13  12   11  10    98    76    54    3210
                                           Rentention Time, minutes
                Figure  2.   Typical Separation of Ethyl Alcohol from Benzene and Toluene

-------
   TABLE  1.   ETHYL ALCOHOL  ANALYSIS GAS  CHROMATOGRAPH OPERATING PROCEDURES
Gas Chromatpgraph:




Detector Type:




Gas Sampling Valve:




Backflush Valve




Sample Loop Size:




Column Temperature:




Detector Temperature:




Injection Temperature:




Carrier Gas:




Carrier Gas Flow:




Hydrogen Gas Flow:




Air Flow Rate:




Column Dimensions:




Column Material:
Perkin-Elmer Model 900




Flame lonization Detector




Seiscor Model VIII (CSV Configuration)




Seiscor Model VIII (BF Configuration)




10 ml




50C




50C




27C




Helium




30 ml/min




40 ml/min




400 ml/min




10' x 1/8" SS




15% TCEP on 60/80 Chromosorb P-AW
                                    A-5 5

-------
1
'.n
AC (-)
AC (0
















i
<

<




s
J
 |



i
i

*



.bK 2.5K 2.5K

NCa a NO NC 9 NO NC   NO NC NO r "
' 4 < 4'
, L -..,.. /,.-- f ~ Q, /..of a r   f ^jt(-_aC V
T T T T J
NU j* NU jl NU>* NU J* "C ' P
^  NC ^ NC ^  NC T * NC 1
i r < \ 1 /*E
k 	 .,,. 	 / c
f *. i r
I \ S , V1-
	 	 !
k...,, 	 1 , .

\ JL L
1 1 '^ \ GSV g> ^
S ______ I , . ^^ ' x
J solenoid^ =>; relay
Q _^, 	 _ g< &|

' 	 11 J
12 1 ' n
p 	 14 J
m J --. ^
13  * f |
* 16  backflush
* 	 ' S) solenoid
ATC S^
Timer
                                                                                                             Aux
                        Figure  3.   Electrical Schematic for Nitrous Oxide Analysis System

-------
      cap
Air Pressure  (30 psi)
  CSV off
Vacuum
      can
Air Pressure  (30 psi)
                                      cap
                                                                1
   P   V

 Backflush
  Seiscor
Backflush off
       Figure 4.  Flow Schematic in Electric Solenoid Valves
                    (Both valves de-energized)
                              A-57

-------
     Gas  Chromatograph

     1.    Perkin-Elmer Model  900  chromatograph
     2.    Soltec  Model B-281  recorder
     3.    Hewlett-Packard Model 3354C GC  computer  system
     4.    Hewlett-Packard Model 1865A A/D Converter
     5.    Analytical column,  10'  x 1/8" SS,  15%  TCEP  on 60/80  Chromosorb  P-AW

     Control Console System

     1.    Seiscor valve - gas sampling configuration
     2.    Seiscor valve - backflush configuration
     3.    ATC timers, Model 3254A346A10PX (2 ea)
     4.    ACSO solenoid valve, Model 834501  (2 ea)
     5.    Brook flowmeter, R-2-15-A w/SS  float,  0-150 scale
     6.    Metal Bellows MB-155 pump
     7.    Female  quick-connect, stainless steel
     8.    Nupro Model 2M stainless steel  regulating valve
     9.    Stainless steel tubing  (0.01"ID)  for capillary restrictor
    10.    Miscellaneous stainless steel,  copper  and Telflon  tubing
          (1/8" and 1/16")
    11.    Miscellaneous stainless steel and brass  unions, tees,  etc.
    12.    Bud Classic II control  console  cabinet,  14" x 19"  panel
    13.    Miscellaneous electrical on-off switches

     SHED Bag Sample Acquisition  System

     1.    Sample pump, Thomas Model 917 CA TFE
     2.    Brooks flowmeter, Model 1555, R-6-15-A,  sapphire float, 0-11 1pm
     3.    Regulating valve, Mupro 4MG, SS
     4.    Telfon tubing, 1/4" OD  x 1/8"  ID
     5.    SS quick connects,  male and female
     6.    Tedlar bag  one cubic  foot capacity
     7.    Miscellaneous nuts, females and assorted unions, tees, etc.

Sample Calculations

     It was initially planned to  use ethyl alcohol blends in normal calibra-
tion cylinders.  During the validation of the calibration technique,  it
became apparent that high pressure ethyl  alcohol blends were not stable and
other calibration techniques were investigated.   Benzene was selected to be
used as the external standard and the relative  response to ethyl alcohol was
established.  Experiments determined that 1 ppm C  (benzene)  was equivalent
to 0.05 mg ethanol per cubic foot.  Using this  relationship, the following
equations were used to determine  grams of ethanol per test.

     1.    General Calculation Equation

          ppm C Ethanol = GC area of Ethanol x ppm C Standard (Benzene)
                                   GV area  standard  (benzene)
                                    A-58

-------
     2.   Ethanol Evaporative Losses

          Ethanol g/test - ppmC (0.050 mg/ppm C ft3) (SHED vol. ft3)  (1 g/103mg)

     If a test used a 68.3 ppm C benzene standard that gave area counts and
the SHED volume was 1708 ft^, then the following rate would be calculated.

          ppm C Ethanol = (3560 area counts, C^HqOH) (68.3 ppm C Q;Hfi)
                                  (17521 area counts,
          ppm C Ethanol = 13.88 ppm C

          Ethanol, g/test = ppm C C2H5OH x Response factor x SHED vol.

          Ethanol, g/test = 13.88 ppm C x 0.050mg/ppm C ft3 x 1708 ft3 x Ig/lOOOmg

          Ethanol, g/test = 1.19 g
 THIS  PROCEDURE  IS  REPRINTED  FROM A  FINAL  REPORT TO  THE  ENVIRONMENTAL
 PROTECTION AGENCY  UNDER CONTRACT NO.  68-03-2377,  "GASOHOL, TBA, MTBE
 EFFECTS  ON LIGHT-DUTY  EMISSIONS."  (Reference  6)
                                  A-59

-------
                      APPENDIX  B
B-l.  DERIVATION OF EQUATIONS  FOR  CALCULATION OF
                EXHAUST EMISSIONS

-------
                                APPENDIX  B-l

        DERIVATION OF EQUATIONS FOR CALCULATION  OF  EXHAUST EMISSIONS


     The derivations are given in the  order  of occurrence of the equation in
Section IV. B. of this report.  Atmospheric values and atomic weight utilized
are :
                    (11)
Standard Atmosphere

     Molecular Wt. = 28.966
     02% by  Vol.   = 20.95  (23.14 by weight)
     02 Mol. Wt.   = 32.000
     N2+ % of Vol. = 79.05  (76.86 by weight)
     N2+ Mol. Wt.  = 28.162

     Where N2+     = Sum of  all elements  other  than oxygen

               (11)
Atomic Weights

     Carbon  (C)    = 12.011
     Hydrogen  (H)  =   1.0079 (use  1.008)
     Oxygen  (0)    = 15.9994 (use  16.000)


     Exhaust Organic  Matter Density:

     Density  =  16.33  g/ft3 for  carbon-to-hydrogen ratio of 1:1.85
     Fuel  Fraction Carbon  for 1:1.85 = (1><12. 011)/( 1><12 .011 + 1.85X1.008) = 0.8656
     HC Molecular  Weight per Carbon Atom = 12.011/FFC
     Density OM =  16.33xRatio of Mol.  Wts.
                =  16.33 ( (12. 011/EFC)/(12. 011/0. 8656))
                =  14.135/EFC g/ft3  (0.4493/EFC kg/m3)

(c) (3)   CO     = CARBON MONOXIDE EMISSIONS
          rriciss

     Hydrogen-to-Carbon Ratio of Fuel  (HCR)

       HCR = Atoms of  H/Atoms of C
           = Ratio of weight amounts in fuel/Ratio  of mol. wt.
           = (FFC/FFO/d. 008/12. Oil)
       HCR = (FFH/1.008)/(FFC/12.011)

     CO Correction for  Water Vapor

       Total H20 = Water Due to Combustion + Humidity

                   HCRxC02c/2
        Therefore :
           CO  =  (1 - 0.01 + 0.005>
-------
(c)(5)   DF = Stoichiometric Percent CO2/Summation of Carbon Containing Exhaust
             Components

     Combustion Balance

       C+H+0+X+02+ N2+ = C02 + H20 + X + N2+

           N2+ = Summation of all components in the atmosphere except oxygen

       Number of Atoms^Relative Weight/Atm. Wt.
       Number of Molecules^Relative Weight/Mol. Wt.


   Therefore:
        FFC  +  FFH  +   FFO    FFX   SAFRXQ.2314    SAFRXQ.7686 _
      12.011    1.008   16.000   MWX      32.000        28.162

        FFC  ^  0.5XFFH   FFX ^ SAFRX0.7686
             T   .-.__.  -j-
      12.011    1.008    MWX      28.162

       SARF = Stoichiometric Air to Fuel Ratio by Weight

   Oxygen Balance  (Number of Atoms)

      2XFFC    0.5XFFH _   FFO  _ 2XSAFR 0.2314
     12.011    1.008    16.000 ~     32.000

     SARF = 11.514XFFC + 34.298XFFH - 4.322XFFO

   Stoichiometric Percent CO?
     SPCO2 = (Exhaust CO2/Total Exhaust)
           = ((FFC/12.011)/(FFC/12.011 + 0.5XFFH/1.008 + FFX/MWX +
              SAFRXQ. 7686/28. 162) )xiOO
           = (FFC/ (FFC + 5.958XFFH + 12. 011XFFX/MWX + 0 . 3278XSAFR) )

   Dilution Factor

     DF = SPC02/[C02c + (OMC  +  COC)X10~4]
     Where :
          OM  = Organic  matter  in ppm carbon equivalent
            C
                                        B-3

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                   APPENDIX C

C-l.  DERIVATION OF ENERGY BASED  FUEL  CONSUMPTION
C-2.  DERIVATION OF EQUATIONS FOR CALCULATION  OF
        EVAPORATIVE EMISSIONS

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                                 APPENDIX C-l

                 DERIVATION OF ENERGY BASED FUEL CONSUMPTION
EBFC = (1/FE)X(3785.4XFDEN/453.6)XLHV
     = 8.345XFDXLHV/FE

Where:
     ESFC   = Energy based fuel consumption, Btu/mile
     FDEN   = Fuel density, g/m
     LHVa   = Lower heating value of the fuel, Btu/lb
     FE     = Fuel economy, mpg
     3785.4 = Conversion from gallon to m
     453.6  = Conversion from pound to gram
 The lower heating value has been used so as to be in agreement with
 the normal usage for engines.
                                      C-2

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                            APPENDIX  C-2

  DERIVATION OF EQUATIONS FOR CALCULATION OF EVAPORATIVE EMISSIONS
M
Where :
MWQM  = Molecular Weight of organic matter per carbon atom
MWAIR = 28.966
Vn    = Net Volume of the Enclosure, ft
DENAIR= 34.69 g/ft3
CT    = 518.7/T;  T = 8
Cp    = PB/29.92  PB = in. Hg

                                         -4
M   = (0.208 MW)xvnx(ppmcxBaro/Temp)xio

Let:
K   = 0.208XMWOM
C   = ppmCXBaro/Temp

Then:       _4
MOM = Kvnxio  (cf - CL)
                                C-3

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TECHNICAL REPORT DATA
(Please read Instructions on the reverse before completing)
1. REPORT NO. 2.
EPA 460/3-83-009
4. TITLE AND SUBTITLE
CALCULATION OF EMISSIONS AND FUEL ECONOMY WHEtv
USING ALTERNATE FUELS
7. AUTHOR(S)
Charles M. Urban
9 PERFORMING ORG \NIZATION NAME AND ADDRESS
Southwest Research Institute
6220 Culebra Road
San Antonio, Texas 78284
12. SPONSORING AGENCY NAME AND ADDRESS
Environmental Protection Agency
Emission Control Technology Division
2565 Plymouth Road
Ann Arbor, Michigan 48105
3. RECIPIENT'S ACCESSION-NO.
5. REPORT DATE
March 1983
6. PERFORMING ORGANIZATION CODE
8. PERFORMING ORGANIZATION REPORT NO.
10. PROGRAM ELEMENT NO.
11. CONTRACT/GRANT NO.
68-03-3073
13. TYPE OF REPORT AND PERIOD COVERED
Final Report (5-82/9-82)
14. SPONSORING AGENCY CODE
15. SUPPLEMENTARY NOTES
16. ABSTRACT
This report provides methods for the calculation of vehicle emissions
and fuel consumption when nonstandard fuels are used. Methods of analyses,
required for evaluation of alternate fuels, are includes by reference or
as Appendices to this report.
17. KEY WORDS AND DOCUMENT ANALYSIS
a. DESCRIPTORS b.lDENTIFI
Air Pollution Emissio
Exhaust Emissions
Chemical Analysis
Motor Vehicle
13. DISTRIBUTION STATEMENT 19. SECURT
Release Unlimited 2Q SECURT
Uncla
ERS/OPEN ENDED TERMS c. COSATI Held/Group
ns Test Procedures
FY CLASS (This Report) 21. NO. OF PAGES
ssified 98
rY CLASS (This page) 22. PRICE
issif ied
EPA Form 2220-1 (9-73)

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