EPA AA-EOD-82-1
                           Technical Report

                              July  1982
                        Gas Divider Evaluation
                                  By

                            Sherman  D. Funk

                                Notice
                                NOTICE

    Technical  reports   do   not  necessarily  represent   final   EPA
decisions or positions.   Their  publication or distribution  does  not
constitute any endorsement  of equipment or  instrumentation  that  may
have  been  evaluated.    They  are   intended   to   present   technical
analysis  of  issues  using data which  are  currently available.   The
purpose in the release of such  reports  is  to  facilitate  the  exchange
of  technical  information and  to  inform  the public  of  technical
developments which may form  the basis for improvements  in emissions
measurement.

                          Engineering  Staff
                   Engineering Operations  Division
                       Office of Mobile Sources
                   Environmental Protection Agency
                          2565 Plymouth Road
                      Ann Arbor, Michigan  48105

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ABSTRACT

    This project  was conducted to evaluate  the  characteristics  of a
gas  divider  used  to  generate   the  calibration  data  for  exhaust
emission  gas  analyzers.   HC,  C02,  CO  and  02 calibration  curves
generated  by  gravimetric  standard  gases  were  compared  with  gas
mixtures  using  the  divider.   The  divider  was  found  to  provide
acceptable  results  of  comparability  for  HC  and  CO.  However,  the
viscosity   of   the   C02   and  02   at   the   higher  concentrations
affected the gas  flow,  which caused a 1-2%  error  in the  theoretical
gas  mixture.   This  report  relates  the  work  that  has been  done  by
this  lab  and others  toward  establishing  a  reliable  dividing  ratio
factor  that  can  be  used   with   C02  and  02   to  achieve  accurate
results when calibrating the analyzers with a gas divider.

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INTRODUCTION

    The  Engineering  Staff  of  EOD investigated  the feasibility  of
using a gas divider  for  generating and/or  checking emission analyzer
calibration standard gases.  Gordon  Becker and  Dave Turner of  the
Gas and  Chemical Analysis  Group  supported  the  Staff by  performing
the  specified  tests.   A  calibration gas  divider  was  loaned  by
National Environmental Systems  of  Livonia, Michigan,  for  these  tests
and evaluation.   The intent of this  project was  to  investigate  and
possibly answer some  of  the questions that have  arisen in  regard to
viscosity  effects  on the  flow  of  C02   gas  through  a  capillary,
thereby causing  an  effect on the  concentration  of the gas  mixture.
The results of  this series of  tests  would be  to  qualify  the concept
and quantify the  calculations needed  to use a divider as  an on-site
curve generator or checker.

BACKGROUND AND THEORY

    The   measurement  of   mobile   exhaust   emissions  requires   a
significant   expense  for   the  acquisition  and  maintenance   of
calibration gases for the  analyzers.  The  use   of  gas  dividers  by
many  laboratories has been  one way  of  reducing  that  cost.  A  gas
divider uses the  principle  of capillary flow to  accurately  divide or
dilute  a  calibration gas  of  known  value   to   set  proportions  by
selecting  combinations  of  capillaries to flow  a diluent  gas  or  a
span gas.

    This  principle  is  expressed   in  the   Hagen-Poiseuille  law  of
capillary flow that states

              Q =    r4    . P1-P2
                    8y         L

         Q =  flow rate
where    y =
viscosity
         r =  radius
         Pl=  inlet pressure
         P2=  outlet pressure
         L =  length

in  this  case,  L,  PI, P2  and  r  are constant.  Thus, Q is  a function
of viscosity y and the formula can be rewritten

              Q =   K
                    y

where    K =      r4 (P1-P2) = constant
                   8L

Using this law the divider ratio can be expressed as follows:

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See  Figure  4 for  capillaries'  flow formula  and flow path  diagram of
the divider.

Since     Q =   K
                y

the formula for divider output concentration is CT= 	Qs	 . Cs
                                                      Qs + Qz

and the divider ratio is related to the number of capillaries flowing

                                                          K
                              by             di =      Ns us
                                                   NS K  + NZ K
                                                      ys      vz

                              or \            di =       Ns
                                                   Ns + Ns-10(jy_s_)
                                                             (yz)

where    Of = Theoretical concentration
         Cs = Concentration of span gas
         Q    = Flow rate
         Ns   = Number of capillaries flowing span gas
         Nz   = Number of capillaries flowing zero gas
         K    = Constant or  TT r4 (PI - P2)
                                   8L
         ys   = Viscosity of span mixture gas
         yz   = Viscosity of zero or balance gas

    The dividers usually use  6-10  "matched"  capillaries  depending on
the  number  of points  needed  to be  checked.  The Model  CGD-11 that
was used in this project contained ten capillaries.

    Many  emissions  testing  laboratories  in  the U.S.  and  foreign
countries  use  gas  dividers  as  a  calibration  tool  for  vehicle
certification and  enforcement  testing  under  the  provisions  of  the
Federal Register  40 CFR  86.114-79 (a)(7).   In  all  cases  that have
been  reported and  reviewed, all units provide  acceptable  results on
all  gases  except  C02  where  in some  instances  marginal  results  of
acceptable accuracy  are  experienced.   It is  generally  believed that
the  viscosity  effects  of   a   C02/N2   mixture   at   the  ranges  of
concentrations in  use  can  cause errors to the point  that  a dividing
ratio  correction  factor must  be developed  (reference  Nissan report
to Andy Kaupert, dated June 23, 1981).  One  of  the  most significant
questions that came  out  of this report  was  the  disagreement between
the  theoretical data derived  from  Wilke's  viscosity  equation for gas
mixtures (reference Journal of  Chemical  Physics,  Vol  18  No. 4, April
1950)  together with  the  Hagen-Poiseuille  law regarding  viscosity and
flow  and  actual  measurements made on  different  concentration levels
of C02«   This report  discussed those tests  and their  results,  and
comments on  possible ways  to relate these data  to the  use  of  a gas
divider.

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EVAULATION TEST PLAN

    Three major areas were addressed  in  assessing  the  gas  divider as
a calibration tool:  1) comparative curves  and  general operation,  2)
capillary  flow   tests  for   viscosity   effects,   and   3)   viscosity
correction factor development.

    Each area is described as follows:

    1.   A gas divider evaluation test which included:

         a.   Comparisons  of gravimetric  versus  divider  curves  of
C02» CO, C3Hs, and Q£ were made to assess accuracy.
         b.   Response measurements were made from time of  gas  valve
change to 90% of full scale and to stable reading on chart.

         c.   A  series  of  runs made  both  in   forward  and  reverse
order to check for hysteresis effects and precision.

         d.   Lowering  the  zero  and span  input pressures  from  25
PSIG (zero)  and  35  PSIG (span) to 15 PSIG  and  20 PSIG,  respectively
to assess pressure affects.

    2.        The   comparison   tests   of   actual   flow   versus
concentration/viscosity consisted  of using  the  flow arrangement  in
Figure  5   in   two   parts.    The  first  was   to run  N2   and  six
concentrations of C02 from 1  %  to 100% at  40  PSIG for a  period  of
1000 seconds  through a Beckman 400  capillary  into  a Brooks prover.
The  prover  is  a volumetric displacement measuring  device  by  which
the  actual  volume  of  gas  is  measured  for  a   specific  time.   The
second part  was to  run the same  C0£  arrangement again and similar
blends  of   02  and  C3Hg.    By  using  actual  volume  and   time
measurements,  flow  rates were calculated.    Theoretical  flow  rates
were derived from viscosity calculations and a  dividing  ratio  factor
for  the  specific concentration.   The  actual  and   theoretical  flow
rates  of  C02,  02   and C3Hg  are  listed   on  Table 9  and  plotted
on Figure 3.

    3.        Measurements and curve data  were analyzed to develop
an  applicable  viscosity  mixture   formula  for  gas   blends.   Wilke's
equation  in  attachment 1  (10),  which used  concentration  ratios,
viscosity  of  individual  gases,  density  and molecular  weights  was
evaluated.   See  Discussion  of  Test   Results   Section  for  symbol
definitions.   This   equation  was  implemented   on a basic  computer
program  in  order  that  these  properties   for  various   gases  and
concentrations could  be entered and the viscosity  mixture  could  be
calculated quickly.

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DISCUSSION OF TEST RESULTS

    The  major  portion  of  this  project  was  to   evaluate  the  gas
divider  for  use as  a calibration  tool.   The  two  issues  that  were
addressed secondarily  were  the  effects  of concentration or viscosity
change on  flow rate  together with  the  investigation  and  search for
an applicable viscosity mixture formula for gas blends.

    The response, hysteresis effect, and  pressure change  checks  gave
excellent results and are expected to cause no problems.

    Other  laboratories  have  run  tests  on  various   models  of  gas
dividers and  have  gotten excellent results.  However,  most  all  have
expressed  a  concern  over   the  apparent  viscosity   effect  on  CC>2
mixtures.   In  order to  see and possibly  quantify   some of  these
effects,   a   series   of  gravimetrically-referenced  curves   was
established   using   0-100   PPM   C3Hg/air,   0-24%    02/N2,    0-5%
C02/N2,   0-15%   C02/N2,   0-1000   PPM   CO/N2   and   0-2500   PPM
CO/N2.   For  each gas  and range the  top gas was run  through  the ten
points of  the divider,  the  response  was  read  on  the  analyzer,  and
the  data  were processed   for  deviation  comparison.   The  curve
comparisons  are  shown  in   Tables  1-8.    The  HC  (0-100  PPM)  was
selected  because it  is  a linear  range on  which  there would be  no
significant viscosity  effect.   A  number of problems were  revealed  in
that a  higher than  expected error  was  seen.   The  curve  appeared  to
be linear.  By  running additional fit and non-zero  intercept  curves,
it could  be  seen that there seemed  to  be a flow,  pressure  or drift
problem with the analyzer and not the fault of  the  divider.  Changes
were recommended to  improve the HC flow controller.

    The  02 was run  to  look  at  viscosity  effect  since the viscosity
of oxygen is  considerably higher than  nitrogen as  opposed to  carbon
dioxide   being   lower.   In  the  case   of  oxygen   the  predicted
(theoretical) and the actual measured deviation from  linear were  in
the  same direction  but  not the  same  magnitude.   It  could be  seen
that  there  were  some  effects  at  the   different  divider  points,
possibly  from viscosity.   See  Figure  1  for divider  ratio  variance
from linear.   The curve for 02  can be seen on Table 4.

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         The formulas used in establishing these plots are:

              CDR = Calculated Divider Ratio
              LDR = Linear Divider Ratio
              MDR = Measured Divider Ratio
              A   = Difference

              Calculated A from linear = CDR - LDR
              Measured A from linear = MDR - LDR

              Calculated %A = CDR - LDR x
                                   LDR

              Measured %A = MDR - LDR x 100
                                 LDR
    where
CDR =
Ns
              where Ns
                    ys
                    yz
                    10

              MDR =
      10 - Ns (jjs) + Ns
              (yz)

           number of capillaries flowing component gas
           viscosity of component gas mixture or span
           viscosity of balance gas or zero
           total number of capillaries
        Ct
    where
        Cp

Ct = Component gas concentration at the top undiluted
Cp = Concentration read at that specific divider point
    Carbon  monoxide  in  nitrogen  C02/N2  curves  were  run  at  two
ranges,  0-1000  PPM and  0-2500  PPM.   CO  was  selected  since  the
viscosities and  molecular weights are mainly  the  same as N2  and no
viscosity effect  should  be  seen.   We again  incurred  a curve  problem
with  the 0-1000  PPM curve  (Bendix).   It  was  8.8%   non-linear  and
could  have  been  defined  better on the  low  end  (Table 5).   However
the  0-2500  PPM  range  (MSA),  Table  6,  showed  a very good fit  and
comparability  down  to  a  maximum  of  + 0.5%  of  point  deviation.   To
prove  further  viscosity or non-viscosity effect, a  range  of  0-10% CO
should be run in the future.

    If viscosity  is a  definite factor,  there should  be considerably
better  comparability on  the  CO   than  C02  or   02«    Carbon  dioxide
in nitrogen curves  were run  in two ranges, 0-5% (table 7)  and 0-15%
(Table  8).   While  a slight  effect  could  be seen  on the 5%  range,
there  was a  significant  effect on  the  15% range with deviations as
high  as  -1.5% of  point.  Also,  for  the  0-15%  range refer  to  the
divider  ratio  comparisons on Figure  2, where  the calculated  ratio is
the  direct  opposite direction as opposed  to measured.   Even  though
the  magnitude  of   deviation  from   linear   was  not  as  great   as
calculated,  it was  greater  than any of  the other  gases run.   An
empirically-derived  curve   of   divider   deviation   from  an   S-Tec
instrument  (Japanese)  was plotted and was  near the  same  magnitude
and direction as the instrument we used.

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    To  better  see  the  concentration/viscosity  curves'  flow  rate
effects,  a   series   of  flow   measurements   were   made  using   an
arrangement  as  seen  on  Figure  5.   Gases  used   were  C02,  CsHg
and  02.   The  results  were  tabulated  on  Table  9  and  plotted  on
Figure  3.   The  theoretical  values  were  calculated  by  comparing
ratios  of viscosity  of  the  various mixtures  to the balance  gas  or
N£.   The  measured values were  derived by a  volumetric displacement
measurement  versus a  time  period  of  flow.   Viscosity  of  mixtures
were  calculated  by using Wilke's  equation  as seen  on  Attachment  1.
The symbols for this equation are defined as:

         X^ = concentration of gas 1
         X2 = concentration of gas 2
         yi = viscosity of gas 1
         U2 = viscosity of gas 2
         MI = molecular weight of gas 1
         M2 = molecular weight of gas 2
         P! = density of gas 1
         ?2 = density of gas 2

    All  the  viscosity  mixture  values   were  calculated  from  this
formula.

    It  is interesting  to note  that for  propane and carbon dioxide
the   theoretical   and   measured   disagreed   in   both magnitude  and
direction, whereas the  oxygen agreed in  direction and very  nearly  in
magnitude.   In  the   curve   comparisons,  the  C02   and  C^Hg  actual
measured deviations were  in  the  opposite direction  of the calculated
based  on  viscosity and  the  02  agreed  in the same  direction.  Some
questions  remain  as  to  why  the  actual flow  rates and  deviations
measured  do  not  agree  with   the  theoretical   and  could  possibly
warrant further investigation.

    The  response  checks  that  were made were  from time   of  valve
change to 90% of full  scale  (3-5  seconds) and  to full stable reading
(10-12 seconds).

    The runs made  in  both forward and  reverse order to  check for any
hysteresis effect  showed no significant effect (+0.2% FS or less).

    Lowering  the  zero and span input  pressure showed no discernible
effect.

    The capillary  flow rate  versus concentration/viscosity  tests are
plotted   on   Figure   3   for  C3H8,   C02  and   02«   The  C3Hg  and
C02 calculated  effects from viscosity do not agree  in magnitude  or
direction with  the measured.   The same  gases  differed in  the same
manner  in the curve comparisons  and will be discussed later  in the
section.  Table 9  lists the values used for the plots on Figure 3.

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    It  has  been  seen  that  different  gases  act  differently  from
viscosity or other effects and that from  the  amount  of  data we have,
it  is  difficult  to state  that  viscosity  is  the sole cause of these
deviations,  although  it  appears  to  be  the  major  cause.   The  fact
that  02 which  has  a  viscosity  considerably  higher  than that  of
N£,  the  balance  gas,  as  opposed  to  CC>2  which  has  a  viscosity
considerably lower  than N£,  yet  both gases have the same  result  in
direction  of  deviation  on  the  divider  causes  some  concern  in
applying the total effect to viscosity.

CONCLUSIONS AND RECOMMENDATIONS

1.  Conclusions

    A.   It can be clearly seen  that,  in  the  ranges  of  gas analyzers
we  use,  the gas  divider  can  be used  as  an  accurate  tool  for
calibration with deviations  of  generally  less than 0.5%  of point  on
all instruments  except  C02 where  a useable divider  ratio  should  be
developed empirically.

    B.   The  instrument   is  easy   to   use   from   an  operational
standpoint,  provides  a  reasonable  response  and  has no  significant
hysteresis effect from forward or reverse order runs.

    C.   This report  is in general agreement with  the Nissan study
report  to  A. Kaupert  dated  June 23, 1981 in that  C02,  which  was
the prime  concern  of  their  study,  has  properties  that  in  actual
practice  will  necessitate  using  an   increasingly  negative  divider
ratio  with  increasing concentration  while  the theoretical predicts
that the ratio should increase in the  opposite (positive)  direction.

    D.   The data  indicate  that  it would not be appropriate  to  use
the available  theoretical formulas to develop  a  divider  ratio.   Any
divider ratio correction should be empirically developed.

2.  Recommendations

    A.   It is recommended  that  a gas divider  be purcahsed and  used
as an alternative gas analysis tool.

    B.   It  is  recommended that  by  testing  this divider,  a  set  of
empirical divider ratios be developed.

    C.   It  is  recommended  that a  plan be  developed  to  implement
these units as a calibration tool for  our analyzers.

    D.   It  is  also   recommended  that   some   additional  work  be
considered in the future to more clearly  define these effects.'

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References
1.       Journal of Chemical Physics, Vol.  18,  Number 4,  April 1950.

2.       Memo and  Report,  Nissan Motor  Co.,  to  Andy Kaupert,  June
         23, 1981.

3.       S-TEC Instruction Manual, Standard Technology,  Inc.,  Japan.

4.       Viscosity Behavior of Gases,  T.  A. Bromley and  C.P.  Wilke,
         Univ.  of  California Industrial  and  Engineering  Chemistry,
         Vol. 43, No. 7, 1950.

5.       Memo to D. Paulsell  from T.  Penninga  re  Horiba  Gas Blender,
         11-1-78.

6.       Memo   to   D.   Paulsell   from  J.   Batchelder,    State   of
         California, re evaluation of Horiba Gas Divider,  5-25-78.

7.       Handbook  of  Chemistry   and  Physics,  Weast  60th  Edition,
         1979-80.

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                          INDEX OF APPENDICES
Table      1       0-100 PPM HC curve (2nd degree fit)
           2       0-100 PPM HC curve (1st degree fit)
           3       0-100 PPM HC curve (non-zero intercept)
           4       0-24% 02 curve
           5       0-1000 PPM CO curve
           6       0-2500 PPM CO curve
           7       0-5% CP2 curve
           8       0-15% C02 curve
           9       Gas Flow Measurement Tabulation

Figure     1       02 Divider Ratio Plots
           2       C02 Divider Ratio Plots
           3       Flow Rate vs. Concentration Plots
           4       Capillary Flow Mixing Method and Formula
           5       Gas Flow Measurement Set-Up
           6       S-TEC Model SED-78 Gas Divider Ratio Plots

Attachment 1       Wilke's Equation for Viscosity Mixture Calculation

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CURVE FIT DEVIATIONS
FROM NAMED/NOMfNrU 7. FROM LAST
'/. POINT 7.
0.011
-0.085
0 . OB8
0.009
0.159
-0. 174
-0. 202
0.047
0.132
0.043

0 . 000
0.011
0 . 008
-0.094
-0. 120
-0.285
-0.468
-0.434
-0.635
-0.418

-0.037

FULL-SCL
0.011
-0.081.
0.078
0.006
0.091
-0.08.S
-0.01.16 '
0.016
0.039
0.012

0.000
0,0.1 1
0.007
-0.075
-O.OH4
-0. 170
-0.233
-0.173
-0. 109
-0.0 (.13

-0.004

rtNL/CYI. CAL
NONE < 4 )
NONE ( 4 )
NONE<4)
NOiNEt 4)
•NC)ME<4>
N(JiME<4>
NONE<4>
NONE ( 4 >
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DATA POINT I <
THE CURVE 1
0.095
0.050
0.000
(4) NO "LATEST" ANALYZER CALIBRATION ON FILE IN THE EFS.
                                                                                                              /
   PRT PI

-------
 PAGE 2
**** PROCESSED:  .1.1:11:37  05-29-82
CAL. NUMBER (UTI)
EQUIPMENT ID NO.
CALIBRATION NAME
TEST SITE NUMBER
END CALIB. AT
MINOR GAS
:   820528111137
:   030284
J   HCAN-CR16
5   A251
:   09:20  05-27-82
:   C3H8
                                             if******************************************
                                             *******************************************
                                             ***                                     ***
                                             *** ANALYZER CALIBRATION CURVE ANALYSIS ***
                                             ***                                     ***
                                             *******************************************
                                             *******************************************
I EPA
I CYL.
I NUMBER
I_

I HH2348
I H89741
I 011829
I G11831
I Gil 852
I H89457
I H89742
I G11857
I H89840
I G11828
I
I BIO
I BO 9
I BOH
I BO 7
I B06
I B05
I B04
I B03
1 BO 2
I B01
I
I— .—
I
I
I

I
1
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
VENDOR
CYLINDER
NUMBER

UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN

UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN


(1)
(1)
(1)
(1)
(!)
(1)
.(1)
(1)
(1)
(1)

(1)
(1 )
(1)
d)
(1)
(1)
(1)
(1)
(1)
<1>

(1) CYLINDER NOT DEFINED
I
I BLEND
I RATIO

I —
I —
I —
T _ __
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IN THE
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I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I
I

92.180
87.605
80.990
62.452
52.481
45.401
39.322
31.688
26.985
24.625

92.180
82.962
73.744
64.526
55 . 308
46.090
36.872
27.654
18.436
9.218

EQUIPMENT

NONE < 1 )
NONE ( 1 )
NONE(l)
NONE < 1 )
NONE(l)
NONE ( 1 )
NONE < 1 )
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FILE SYSTEM
I
NEW I
CURVE I
.1
91.876 I
87.282 I
80.897 I
62.476 I
52.645 I
45.433 I
39.369 I
31.835 I
27.149 I
24.761 I
I
91.876 I
82.781 I
73.593 I
64.451 I
55.218 I
45.984 I
36.842 I
27.609 I
18.467 I
9.280 I

ANALYZER DEFL .
MEAS. CORR.
X X
	
100.000.
95.000
88 . 050
68.000
57.300
49,450
42.850
34.650
29.550
26.950

100.000
90.100
80.100
70.150
60.100
50.050
40.100
30.050
20.100
10.100

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100.000
95.000
88.050
68.000
57.300
49.450
42.850
34.650
29.550
26.950

100.000
90.100
80.100
70.150
60.100
50.050
40. 100
30.050
20.100
10.100

1
I
I

I CYL
ICYI,
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
I
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
ICYL
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1
AVERAGE INPUT
DEVIATION
FROM
DATA TYPE

CURVE
CURVE
CURVE
CURVE
CURVE
CURVE
CURVE
CURVE
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CURVE

TO BE
TO BE
TO BE
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INPUT
INPUT
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INPUT
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NAMED
NAMED
NAMED
NAMED
NAMED
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NAMED
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NAMED

DATA POINT
THE CURVE
I
I
I
—
I
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I
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1
I
I
I
I
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I
CURVE FIT DEVIATIONS I
FROM NAMED /NOMINAL 7. FROM LAST I
7. POINT 7. FULL-BCL ANL/CYL CAL I

-0.331
-0.370
-0.115
0 . 038
0.312
0.070
0.119
0.462
0.606
0.548

-0.331
-0.219
-0.205
-0.116
-0.164
-0.230
-0.080
-0.164
0.169
0.663


0.297

-0.3 31
-o.:'5Si
-0. 1.01
0.026
0.179
0.035
0.051
0.160 '
0.179
0.148

-0.331
-0 . 1 98
-0. 164
-0.081
-0.098
-0.115
-0.032
-0.049
0.034
0.067


0.156

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0.000

I
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(4) NO 'LATEST' ANALYZER CALIBRATION ON FILE IN THE EFS,
 C OVTBN01
 ILLEGAL COMMAND

-------
 PAGE
**** PROCESSED:  07:37:03   05-29-02
     CM.... NUMBER  (UTt)
     EQUIPMENT  10  NO.
     CALIBRATION  NAME
     TEST SITE  NUMBER
     END CALIB. AT
     MINOR GAS
020528093703
039284
HCAN-CR16
A251
07:20  05-27-82
C3H8
*>K**>!c#>|<****;i<**#****#****#********:t:)t:** ******
*******************************************
***                                      ***
*** ANALYZER CALIBRATION CURVE ANALYSTS ***
***                                      ***
********************************* ***#**'!'*;»:*
********************************* *** + .******
I EPA
1 CYL.
I NUMBER
T _- -
J.
I MH2348
I H 1.197 41
I fiiict :>•;•
I G 1 1 8 .5 1
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i mm; 40
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97. A 05
00.990
62.452
52.481
45.401
39,322
31 .688
26 . 985
24.625

92. 180
82,962
73.744
64.526
55.308
46.090
36.872
27.654
18.436
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92. 099 I
87.478 I
81.055 t
62.524 I
52.635 I
45.380 I
39.280 I
31.702 I
26.988 I
24.585 I
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73,707 I
64.511 I
55.223 I
45.935 I
36.739 I
27.450 I
18.254 I
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ANALYZER DEFL.
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X X
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95.000
88.050
68.000
57.300
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42.850
34.650
29.550
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90.100
80.100
70.150
60.100
50.050
40.100
30.050
20.100
10.100



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100.000
95 . 000
88.050
68.000
57.300
49.450
42.850
34.650
29.550
26.950

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90.100
80.100
70.150
60. 100
50 . 050
40.100
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I
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AVERAGE INPUT
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CURVE
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0.293
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0.012
-0, .162

-0.088
-0.015
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-0.023
-0. 154
-0.338
-0.363
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0.109
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(4) NO 'LATEST" ANALYZER CALIBRATION ON FILE IN THE EFS.
                                                                                                                         J

-------
 PAGE 2
*#** PROCESSED:  10:57:50  06-03-82
     CAL. NUMBER (IJTI)
     EOUIPMENT ID NO.
     CAL I BRA [.TON NAME.
     TEST SITE NUMBER
     END CALIB. AT
     MINOR GAS
        820603105750
        03806A
        OXGA-CR26
        A251
        1A:00   OA-02-82
        02
*******************************************
***                                     ***
*** ANALYZER CALIBRATION CURVE ANALYSIS ***
**#                                     *#*
*******************************************
*******************************************
I EPA
I CYL.
I
I
I NUMBER I
I A 53 36
I A3424
I E2695
I A15l::i8
I A5443
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UNKNOWN
UNKNOWN
UNKNOWN
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UNKNOWN
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UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN

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14.341
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9.561
7.171
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EQUIPMENT


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23.882 I
18.276 I
14.749 I
9.922 I
4.772 I
3.098 I
I
20.904 I
23; 920 I
21.404 I
18.977 I
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14.1.48 I
11 .797 I
9.372 I
7.047 I
4.722 I
2.373 I
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TEM . 1
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ANALYZER DEFL .
MEAS . CORR .
X
95.500
73.100
59 . 000
39.700
19.100
12.400

83 . 600
95.650
85 . 600
75 . 900
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47.200
37.500
28.200
18.900
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73.100
59.000
39.700
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95.650
85.600
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47.200
37.500
28.200
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I
AVERAGE INPUT
DEVIATION
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I CURVE FIT DEVIATIONS I
DATA TYPE I FROM NAMED/NOMINAL 7. FROM LAST I
I '/, POINT •/.
f
CURVE
CURVE
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INPUT I
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NAMED 1
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NAMED I
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-0.084
0.1 28
0.001
0.079
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0.075
-0.504
-0.766
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-2.019
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-0.000
0.094
0.000
0.031
0.010
-0.056

-0. 185
0.071
-0.431
-0.501
-0.575
-0.771
-0.61 5
-0,756
-0.496
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0.132
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I
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(4) NO "LATEST" ANALYZER CALIBRATION ON FILE  IN  THE  EFS,
   pro: PI
 SET THE TERM IN AL-
TO THE TOP OF PARE AT THE BEGINNING OF EACH REPORT PAGE

-------
 SET THE TERMINAL  TO  THE TOP OF PARE  AT  THE  BEOTNNINO OF EACH REPORT PARF
 PRESS   TO START PRINTING.   PRESS    OR
 PAGE 2
                                    -(.:>   TO PREVENT PPTNTTNfi.
Me*** PROCESSED:   09:45:03
     CAL. NUMBER  MITT)
     EOUIPMENT  ID NO.
     CALIBRATION  NAME
     TEST RITE  NUMV-FR
     END CALID. AT
     MINOR GAK
                           R20A08094503
                           03R5A3
                           CO AM -TR1.9
                           A 251
                           09!00  0A-07-82
                           CO
ft*************************** •»******. A* ***•(:**
***                     '                  ***.
*** ANALY7ER  CALIBRATION  CIIRUF AWAI YSTR ***

# A************************ ********•*:*. **.*:*.<:«•#
####**#*#*****#**#***#*****A*:*** t****;M. *;«**
1 	
I EPA
I CYL.
I NUMBER
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I A7200
I A2825
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I A 10078
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I
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I B01
I
I
I
I
-
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I
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UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
UNKNOWN
IIK'KNOWr

T 	 	 - 	
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I
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I
I
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NOMINAL
9A9.02
827.00
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477.01
4 1 A . 20
357 . A3
299. A8
238.42

9A9.02
872.12
775.22
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581 .41
494.51
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290.71
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FOUTPMENT


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43.800
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0,234
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-------
                                                      SYSTEMS RF.AL-TIME MON1TOR-6.1
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* • «                                         * * «
•*» ANALYZER CALIBRATION  CURVE ANALYSIS »**
* A It                                         * * *
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I 22B0.6 NOMEfl
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ANALYZER DEFL. I I CUKVE FIT DEVIATIONS
MEAS. CORK. I DATA TYPE I FROM N AKEO/NOMI N AL X FROM LAST
X XI
91.250 91.250 ICYL CURVE INPUT
7b.5bO 76.^50 ICYL CURVE INPUT
68.300 66. SOU ICYL CURVE INPUT
61.100 61.100 ICYL CURVE INPUT
52.350 52.150 ICYL CURVE INPUT
11.350 11.350 ICYL CURVE INPUT
35.600 35.t>00 ICYL CURVE INPUT
28.500 28.500 ICYL CURVE INPUT
1
91.250 91.d50 ICYL TO HE NAMED
82.850 82.B50 ICYL TO BE NAMED
71.500 71.500 JCYL TO BE NAMED
66.150 66.150 ICYL TO BE NAMED
57.300 57.300 ICYL TO BE NAMED
40.100 18.100 ICYL TO BE NAMED
39.000 39.000 ICYL TO Bf NAMED
29.600 29.800 ICYL TU BE NAMED
20.100 20.100 ICYL TU BE NAMED
10.150 10.150 ICYL TO BE NAM£0
1

AVERAGE INPUT DATA POIN1
DEVIATION FROM 1 HE CUKVE
X POINT X FbLL-Sr.L ANL/CYL CAL
0.051 0.019 NONtd)
-0.212 -0.157 NOMEd)
0.155 0.101 NONEd)
-0.011 -0.025 NONE(I)
0.170 0.081 NUNEd)
-0.159 -0.061 NONEd)
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-0.257 -0.208 NUNEd)
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-0.032 -0.017 NONEd)
0.183 O.OH3 NONEd)
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0.158 0.011 NONEd) I
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___.__.._-._-_.__.._.--__-..__-..._____-.---_-_----- 	 . 	 ....... T
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0.060
0.007
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0.202
0.063
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-------
 PAGE 2
**** PROCESSED:
CAL.
EQUIPMENT  TO
CAI. IBRiVi I ilf-l  i-
TEST SITF  ?•".;•
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I


CONCENTRATIONS
KLEND I NAMED OR
K A l.i II I
- . - 'I
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14.360
13.577
1 1. i 550
10.303
8.675
6.719
5.141
4.637
3.848
3 . 005
1,454

0 . 000
14.360
12.924
11.488
10.052
8.616
7.180
5.744
4 . 308

2.872
1.436

IN THE EQUIPMENT


LATEST
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CURVE I
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14.360 I
13.581 I
11.532 I
10.320 I
8.673 I
6.718 I
5.139 I
4.635 I
3.854 I
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9.992 I
8.523 I
7.078 I
5.664 I
4.243 I
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ANALY/ER DEFL. . I
MEAS.
X
- M —
90.000
85.900
74.700
67.800
58.100
46.100
36 . 000
32.700
27.500
21.700
10.800

0.000
90.000
82.300
74.150
65.900
57.200
48.350
39.400
30.100

20.600
10.600

CORR. I
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C* T
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90.000 ICYL.
85.900 ICYL
74.700 ICYL
67.800 ICYL
58.100 ICYL
46.100 ICYL
36.000 ICYL
32.700 ICYL.
27.500 ICYL
21.700 ICYL.
10.800 ICYL
I
0.000 ICYL
90.000 ICYL
82.300 ICYL
74.150 ICYL
65.900 ICYL
57.200 ICYL
48.350 ICYL
39.400 ICYL
30.100 ICYL.
I

I'
DATA TYPE I
I
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CURVE INPUT I
CURVE INPUT I
IMJRUF INPUT I
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CURVE INPUT M
CURVE INPUT I
CURVE INPUT I
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10.600 IOTHER CYL. PT. I
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I
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-0.001
0.032
-0. 155
0. 165
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-0.041
0.159
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-0,012
0.038
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0.004

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-0.001
-0.081
-0.330
-0.365
-0.567
-0.622
-0.490
-0. -100

-0. 183
-0.055


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(4) NO  "LATEST'  ANALYZER CALIBRATION ON FILE  IN  THE EPS.
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 SET THE TERMINAL 70 THE TOP  OF PAGE AT THE  BEGINNING OF EACH REPORT PAGE
 PRESS  TO START  PRINTING.  PRESS     OR   TO PREVENT PRINTING.

-------


02%
0
3.112
9.914
18.253
23.903
99.5
100

C3H8%

0
0.833
2.069
15.097
99.7
100%

C02%
0
0.9503
2.113
4.351
8.28
14.36
99.99
100
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100
96.888
90.086
81.747
76.097
0.50
0

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99.167
97.931
84.903
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0

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99.049
97.887 >
95.649
91.72
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VOLUME
(CO
1000
1000
1000
1000
1000
1000


11

1000
1000
1000
1000
1000
1000


1000
1000
1000
1000
1000
1000
1000

MEASURED
TIME
(SEC)
104.90
105.05
105.47
106.12
106.75
112.66


"

104.39
104.60
104.86
108.00
121.20



105.7
105.8
106.1
106.7
107.5
109.5
129.5

THEORETICAL
FLOW RATE
(Q)CM3/SEC
9.533
9.519
9.481
9.423
9.369
8.876


'*

9.579
9.560
9.536
9.259
8.251



9.461
9.451
9.425
9.372
9.302
9.132
7.722

VIS (umix).
POISE @ 21 C
.1760 E-3
.176953 E-3
.1788015 E-3
.1815293 E-3
.1832114 E-3
.2044667 E-3
.206064 E-3

"

.1760 E-3
.1735742 E-3
.1701142 E-3
.141585 E-3
.0803749 E-3
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.1760 E-3
.175349 E-3
.1746291 E-3
.1732498 E-3
.1709951 E-3
.1678784 E-3
.148001 E-3
.1480 E-3
RATIO
umix-UN2
0.0
0.9946
0.9843
0.9695
0.9606
0.8607


ft

0.0
1.013
1.035
1.243
2.190



0.0
1.003
1.007
1.016
1.029
1.048
1.189

RATIOxQN2
CM3/SEC
9.533
9.482
9.383
9.243
9.158
8.206


ft

9.579
9.713
9.910
11.907
20.130



9.461
9.495
9.535
9.611
9.738
9.919
11.251









NOTE: The viscosi-
ties of the gas
mixtures were
calculated using
Wilke's equation 10
from the Journal of
Chemical Physics,
Volume 18, Number 4
April 1950, "A Vis-
cosity Equation for
Gas Mixtures".








Table 9

-------
     O
    .01
V
V
i


     ...
    .U/i
              ! i
               i i

                  (]
1 !-
                        ~r-
          I
                                 TT
                                   ! I
                                  I I
                        tl
                                              i i
~r
                            T+f-
                           
                                                                                                                 \
                                                                                                                 \

        M    (')
        (•I    ( J
                                in    co
                                                              ro    cxj
                 3        ^
                                                                            7
                                              9
                                                                                                               C'J    I I

-------
y
/
3<

-------

-------
                     Capillary Flow Mixing Method
Cm
                   Q2
                 ./vvv\_
Qi
.cs
            Ql + Q2
                                  CM
                            Ql
                          ./VVW.
Cm =     concentration of mixture out

Cs =     concentration of span or component gas

CZ =     concentration of zero or balance gas

Ql =     Flow rate of balance gas

Q2 =     Flow rate of component gas
                                                             Figure  4

-------
'-Of

-------
                      C02  High Concentration Calibration Curve

                   __f pr_ S-TEC_ ?.:odol  SG5-78 _Sj.;ir,d^rji C-*  D1 vi fjg

u;::'i--.!-:;J:": :.. ;::..V±L'..::.
f^JiL:.::-::-  « •• v 71". :..:::.•:.  '
^r^iCto- full_scale)_
       -0.

          34-


                            	          .     •;.- - -i • -::-•;-••: •<-•••• •• •  ..•\^-.- }•
               •  This "curve 'shows "applicable' calibration curve-" when hicjh"Concenti'atiort

                     ' staiidaTd-ga5"i'?"us'eit'l:oir.';rodqr-SGD=7S-Standa-rd- Gas-Dividcr-r
      o ID* i\'.
               ~i P'OTian  inr-tanccr '-vhcn'fi standard"ints-of !&?&• CO^ is-uscd-and-thc •	
                  vidinv^-iacror-is-soi -at- 5,—thc-coriC-c-.tration-ratio— rc.iil*- as-0-f'0t>
.i.-frum the  curve, ao thru the  conccncrucion  which is  actually  generated-.A j,L
  determined fi-om 10 x O.if.'Go = S.L't",")^.
                                                   STANDAT\D  T^CJINOT.f)C',V  INC
                                               -      ..     Kvnrrn.  -IAI-.'.:;

-------
518
C .   R .  \V I L K E
  * All data at atmospheric pressure.
  • M. Trauu and H. E. BenUele. Ann. d. Phytik 5. 561 (1930).
  » M. Trauu and K. F. Kipphan. Ann. d. Pliysik 2. 743 (1929).
  • M. Trauu and A. Melster. Ann. d. Physik 7. 409 (1930).
  « M. Trauu and K. G. Sore. Ann. d. Physilt 10. SI (1931).
  •J. \V. Buddenbers. M.S. thesis.  University oi California (1948). Data
determined relative to Ns.
  ' M. Trauu and F. Kurz. Ann. d. Physik 9. 992 (1931).


bined* to eliminate the  diffusion coefficient  from  the
                        1*1
     1+-
     1+
                                                    (10)
              To offer a severe test of Eq.  (11) a number of binary
           systems exhibiting highly irregular and dissimilar vis-
           cosity-concentration  curves  were  selected  from the
           literature. These data are plotted and compared with
           the calculated curves in Fig. 1. Properties of the pure
           components and literature  sources for these  systems
           are given in Table I. It is believed that the close corre-
            pbndence between these calculated and observed data
           indicates the ability  of Eq.  (11) to  reproduce gas
           viscosity behavior with  sufficient  precision for  most
           purposes. The average  deviation  between calculation
           and experiment for the data shown in Fig. 1, excluding
           terminal points, is 0.97 percent. Prediction of the hy-
           drogen-argon curve is the least satisfactory, and by ex-
           cluding these data the average deviation between calcu-
           lated and experimental points is reduced to 0.49 percent
For ideal gas behavior, Eq.  (10) may be reduced to the
relatively simple expression:
                                                                    240
Equation (11) constitutes the final recommended rela-
tion  for  binary  mixtures.  This relation  is relatively
convenient to use, requiring only the molecular weights
and viscosities of the pure components for the predic-
tion  of  the  entire  viscosity concentration curve.  It
should be noted that the equation contains no empirical

  • Values of ft; and 5: need not necessarily be viewed as equal
to a single value of 3 in corr.binini; (3) and' (9;, hut rather that
l3 = 3\, in Calculating D;-.. and ^ = 3: ir. calculating D-\.  Thus it is
possible that errors due to deviations  between 0i and £» may for-
tuitously cancel in each of the partial viscosity terrus in (3).
                                       Colculoled Curves
                               0 0 £ '+ •• Eiperirrientol Dot a
                              .2     A     .6     .8     1.0
                                Mole Fraction of Firs! Gas

                 Fic. 1. Comparison of calculated and experimental
                        viscosities for some binary mixtures.
w> 1O
TABLE I.

Gas pair
He-A
NVO-
C;Hc-C>Hs
H-CCi:F.
H-C»H,
HrA
Ne-A
Xe-He
He- A
XYCO:
HrCO:
HrNt
Ne-CO.
Xe-CCl:F.
Xe-X.
COrCCl.F;
XrCCljF.
Properties of gases used in Fig.

,oc
.20
27
250
25
26.9
20
200
200
200
25
25
25
25
25
25
25
25



1 and Table II.'


TABLE II. Calculated and experimental data for
: muiticomDonent mixtures.

it\ X101 M:X10* *» . *r viscosity data
197.3
178.1
152.6
SS.4
89.1
87.5
422.0
422.0
267.2
176.8
S8.4
8S.4
313.3
313.3
313.3
176\8
221.1
205.7
136.3
124.0
81.7
221.1
320.8
267.2
320.8
147.8
147.8
176.8
147.8
124.0
176.8
124.0
124.0
2.417
0.994
1.276
3.943
3.674
1.S70
1.606
0.4862
2.318
1.368
2.470
1.903
2.250
3.987
1.612
1.751
2.358
0.2716
1.014
0.779
0.0920
0.1539
0.23S4
0.6166
1.552
0.2789
0.7281
0.1977
0.2750
0.5011
0.2628
0.6552
0.5351
0.3830
a,b
c
d
e
f
a
a
a
a
e
e
i.°C Ne




Volume percent 01
A He H:


components
CO: X: CChF.
200 31.93 32.13 . 35.94
25 33.33
25
25
25 25.00
25

• See Table I
» See Tabie I





. reference b.
. reference e.

numerical constants,


the kinetic

theory-

33.33
33.33
25.00
25.00



the


33.33
33.33 33.33
33.33 33.33 33.33
25.00 25.00
25.00 25.00 25.00




Viscosity X101.
"calc ^exp
360.0 3S7 4.
190.2 18j!7» !
145.7 Hb9a {
144.6 Usi8» '
159.3 168 >
146.7 U7!l»



constant 4/V2 coming from


1

COMPARISON OF CALCULATED WITH
EXPERIMENTAL DATA

-------


02%
0
3.112
9.914
18.253
23.903
99.5
100

C3H8%

0
0.833
2.069
15.097
99.7
100%

C02%
0
0.9503
2.113
4.351
8.28
14.36
99.99
100
GAS

N2%
100
96.888
90.086
81.747
76.097
0.50
0

N2

100
99.167
97.931
84.903
0.3
0

N2%
100
99.049
97.887
95.649
91.72
85.64
0.01


VOLUME
(CO
1000
1000
1000
1000
1000
1000


11

1000
1000
1000
1000
1000
1000

(I
1000
1000
1000
1000
1000
1000
1000

MEASURED
TIME
(SEC)
104.90
105.05
105.47
106.12
106.75
112.66


M

104.39
104.60
104.86
108.00
121.20


it
105.7
105.8
106.1
106.7
107.5
109.5
129.5

THEORETICAL
FLOW RATE
(Q)CM3/SEC
9.533
9.519
9.481
9.423
9.369
8.876


11

9.579
9.560
9.536
9.259
8.251


ti
9.461
9.451
9.425
9.372
9.302
9.132
7.722

VIS (Umix)d
POISE @ 21 C
.1760 E-3
.176953 E-3
.1788015 E-3
.1815293 E-3
.1832114 E-3
.2044667 E-3
.206064 E-3

i*

.1760 E-3
.1735742 E-3
.1701142 E-3
.141585 E-3
.0803749 E-3
.08029 E-3


.1760 E-3
.175349 E-3
.1746291 E-3
.1732498 E-3
.1709951 E-3
.1678784 E-3
.148001 E-3
.1480 E-3
£/ RATIQ4/
ifmix-jjNJ
0.0
0.9946
0.9843
0.9695
0.9606
0.8607


f*

0.0
1.013
1.035
1.243
2.190


ii
0.0
1.003
1.007
1.016
1.029
1.048
1.189

' !/- (L<
RATfl5xON2
GM3/SEC
9.533
9.482
9.383
9.243
9.158
8.206


"

9.579
9.713
9.910
11.907
20.130



9.461
9.495
9.535
9.611
9.738
9.919
11.251

sty/ /•S £ ^~








NOTE: The viscosi-
ties of the gas
mixtures were
calculated using
Wilke's equation 10
from the Journal of
Chemical Physics,
Volume 18, Number 4
April 1950, "A Vis-
cosity Equation for
Gas Mixtures".









Table 9

-------
      UNITED  STATES ENVIRONMENTAL PROTECTION AGENCY
                     ANN ARBOR. MICHIGAN  48105
                                                                OFFICE OF
                                                          AIR. NOISE AND RADIATION
                             June  18,  1982
SUBJECT:      Gas Divider Evaluation

   FROM:      Sherman D. Funk         tp"'
              Engineering Staff

MEMO TO:      C. Don Paulsell
              Chief, Engineering Staff
    An evaluation  project  and report have been completed  on the gas
divider for use as a calibration device for our exhaust analyzers.

    It has  been  determined that this type of  instrument  may be used
instead of  a full  complement of gas  cylinders to  produce  accurate
calibration  curves.   An  empirically-established  divider   ratio  is
needed  for  C02-   Use  of  a  divider  can  result  in  considerable
savings in  manpower and funds.   Potential  accuracy  is on  the order
of +0.5% of point.

    It  is  recommended  that  EOD  pursue  the  development  of  new
analyzer calibration procedures using the gas divider.

    A copy  of the  report on this project  will be circulated and will
be  available  from  the   Gas  &  Chemical   Analysis  Group  or  the
Engineering Staff.

cc: G. Reschke
    J. Carpenter
    R. Lawrence
    R. Gilkey
    K. Heiss

-------