EPA-AA-EOD-80-12
                             Technical  Report
                              December,  1980
                            EVALUATION OF THE
                         BECKMAN  951A ATMOSPHERIC
                               NOx ANALYZER
                                    by
                             Sherman D. Funk
                                  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 evalu-
ated.  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
                   Mobile Source Air Pollution Control
                     Environmental Protection Agency
                            2565 Plymouth  Road
                        Ann Arbor, Michigan 48105

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                          Abstract
The primary  method used for  the measurement of  NOx  emissions by
EPA and the  automotive  industry  is  by the chemiluminescence proc-
ess.   Several  improvements have been made  in  these  instruments
since the original vacuum  type NOx  analyzers.    EPA has taken the
opportunity to evaluate some  of  these instruments in an effort to
refine its analysis capability.

Although other instruments have  been  evaluated  in various degrees
by  EPA  and the  industry,  this  report discusses  the  Beckman  951A
which has a history of wide usage and  previous evaluations.

Bench  testing  and operational comparisons  were  completed  in the
EPA  laboratory  over  a  period of six  weeks.   Although  the  951A
still demonstrates need  for  improvement  in  certain  areas,  it met
all  EPA  requirements  and  advertised  specifications.   The   test
results correlated to within  _+0.5%  of full  scale to  the presently
used  Teco 10A.   The  951A has  been  found  to  be  an  acceptable
alternative to the vacuum type chemiluminescence  analyzer.

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  I.   INTRODUCTION

      The NOx analyzer evaluation project on  which  this report is writ-
      ten is the result of earlier investigations into improved state of
      the art  instrumentation  for  the  analysis  of  vehicle  NOx  emis-
      sions.  These investigations led to the Beckraan atmospheric NO/NOx
      analyzer.   Two Beckman versions  (the 951  and  the  951A,) have been
      evaluated  at this laboratory.   Since the 951A has  been tested to a
      greater degree it will  be  the one addressed in this report.
 II.  BACKGROUND

      EPA EOD  has used  the vacuum  type  NOx  analyzers  for  Light  Duty
      vehicle emission testing since 1972.   The  vacuum pumps associated
      with the' Teco   10A  models  have been  a  constant  source  of main-
      tenance problems and a potential  cause of leaks.  In addition, the
      use of pure oxygen  for  ozone generation has  always  been  a safety
      concern.   These problems and  concerns as well  as  the development
      of the atmospheric NOx analyzers,  prompted the search for a better
      instrument to measure  NOx.

      In the past few years,  a number of  atmospheric NOx analyzers have
      been advertised  and considered by  the  EPA  laboratory.  However,
      only  a  few have  ever had  extensive  evaluation.   One   was  the
      Philco-Ford version.  The  report,  completed in June 1974  indicated
      it was an acceptable  instrument  for  light duty vehicle  emissions
      testing.    Inquiries  to industry  laboratories  revealed  that  the
      Beckman  951 had  also  been  extensively  tested and  used  in  the
      industry.  These data, coupled with  our limited resources to eval-
      uate instruments in general, prompted us to  select  the  951 for a
      more thorough  evaluation.   A  Beckman 951 was purchased  and  was
      tested  for a  period   of  time.   However,  during  the  evaluation
      period the  newer  version  the  951A,  was developed.   Although  the
      basic detectors are unchanged,  the  951A  utilizes  improvements in
      flow control and  regulation.   The  company  claimed the  951 could
      not be upgraded to  a  951A configuration, but  provided  a  951A for
      additional  testing.   The   following  test  plan  was  developed  to
      assess  the performance of   the  951A  relative  to  our   current
      instrumentation.
III.  TEST PLAN

      A test  plan to evaluate  this  instrument was  designed  and imple-
      mented in three parts.

      A.  Preliminary Checkout
          A basic analyzer checkout procedure  was  preformed  in a speci-
          fically designed equipment test  rack  by the  following steps.

              1.   Stability,  Noise,  Speed  of Response, and Repeatability
                  checks were made by  performing the  following:
                                  -2-

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                 a.   Select 0-100  PPM  range on  the instrument  and an
                 appropriate span gas.

                 b.   Alternatively  pass zero  and span gas  through the
                 instrument while  in the NOx position  of  the converter
                 for  a  period of 75  seconds each.

                 c.   Using a  stopwatch, measure  the  time  from  a gas
                 input  change until  reading indicates 90% of full scale.

                 d.   During  these  tests  observe  traces  for  noise,
                 stability, and repeatability.

             2.   Using  procedure given  in manual,  set pots  for  range
                 attenuation compatability.

             3.   Perform  standard  procedure  for converter  efficiency
                 checks.

             4.   Run  a  curve check  on  the  0-100 PPM and  the  0-250 PPM
                 ranges and process  data.

             5.   In  order to check  flow sensitivity,  perform  the  fol-
                 lowing tests.

                 a.   With the  instrument adjusted for normal operation,
                 pass a span gas through the instrument for 45 seconds.
                 b.   Record reading  on  the chart  recorder.
                 c.   Adjust  instrument  by-pass flow up to  2400  CCM and
                 down to  400 CCM in  200  CCM steps.

         Comparison Tests
         The Beckman unit was  plumbed  into the  auxiliary  by-pass  line
         of the  Teco  10A  system in Analysis  Site A001.   A series of ten
         FTP and two  HWFET was run.  These  produced 64 sample bag  com-
         parisons from  actual certification tests.

         C02 Interference Test
         Two sets of  four mixtures of NOx  and  C0£  were  blended and
         then measured  on the Teco  10A  and the 951A both  in the NOx and
         the NO modes (see Appendix C). The Teco 10A was  assumed  to be
         interference free.
IV.   SUMMARY OF RESULTS

     The results of our tests  can be  summarized as  follows:

     A.   Speed of  response  -  Time from external valve  change (zero to
         span) to  90%  FS-Fast response  switch  position  - 6.3 sec; Slow
         response  switch  position -  10.4  sec.  Installed  in Analyzer
         bench  -  Fast response  switch  position   -  11.4   sec.   Slow
         response switch position -  15.8 sec.
                                 -3-

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B.  Attenuation Accuracy - Ability to  match  measurements from one
    range to another was less  than _+0.5 of  full  scale error.

C.  Converter  efficiency  at  final  temperature  setting  (601°  F)
    98.15%.  Converter has a fairly  flat response curve within the
    operating range (See Appendix E).

D.  Linearity  -  -0.4%  non-linear on  0-100 PPM  range;  +0.1% non-
    linear on 0-250 PPM range.

E.  By-Pass Flow Sensitivity  -  No  change  in  output  while by-pass
    flow was  changed  from 400 CCM to  2400 CCM in  200  CCM  steps.
    Sample pressure remained the same.   However, a 0.1 PSIG  change
    in sample pressure caused a  1.0% of  full  scale change in out-
    put of analyzer in the same  direction.

F.  Precision  -  Zero and  span   settings were repeatable  to less
    than ±0.5% of full scale.

G.  Noise  (degree  of  random  and periodic deviations  of output)
    average peak to peak - noise was no  greater than 0.3% of full
    scale.

H.  Stability  -  Zero  and span drifts  were less than _+!% of full
    scale for a period of four hours of continuous  runs.

I.  Comparison tests  to  Teco  10A -  64  comparisons produced  a mean
    difference of  +0.33 PPM.   These  were no greater  differences
    than   0.7   PPM    (See   Appendix   B).    Corrected    sample
    (Sample-Background) values from  these same tests were compared
    and correlated to a mean difference of +0.04 PPM  (See Appendix
    B 1).  A series of  10 blended SAC  bag  measurements  resulted in
    differences of less than +0.'j PPM.

J.  Response  to  C02  -  Response to  CC>2 was  less  than  1  PPK  at
    concentrations   near  the top of  the  C02 operating  range for
    light duty emissions.  (See  Appendix  C).

K.  There are a number of potential problem areas with  the Beckman
    951A:

    1.  The extensive use ot  miniature  thin  wall  teflon tubing in
        the   unit,   some  areas   in   which   (capillary  tubing,
        especially)  inadvertent  pinching  or  damage  could   cause
        abnormal operation.   Capillaries   should  be  made  of some
        kind of hard material.

    2.  It is difficult to make  the NO bypass  flow balance adjust-
        ment  using  the NC^-free NO gas  method  since  opening and
        closing  the  door  cause  a 0.5% difference  in  output.  The
        door must  be  opened and the HV  interlock set  to make an
        adjustment  with  the  bypass  compensator valve.   It   is not
        known  why  this  door  causes  a  difference   in  output.
                            -4-

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             Another area,  which  may be  part  of the  problem,  is that
             the sample  capillary is  positioned so  that  closing the
             door  presses  against   it.    This   could  possibly   affect
             capillary  flow.  This has not  been  proven,  but the  design
             should be  improved.

         3.   Higher  temperatures   of  the  converter  cause  different
             responses    at   different   concentrations   causing   some
             apparent non~;inearity.   It is not  known  why this occurs.
             It is recommended to run at  the  lower  end of the tempera-
             ture operating  range.

         4.   The NO bypass valve knob kept coming loose although  it was
             re-installed a  number  of  times.    Also,  the  NO/NOx mode
             switch  kept  coming  loose  even  though  it   was  tightened
             repeatedly.

         5.   The sample flow rate came  no where  near 200 CCM at  4 PSIG
             as the manual  recommends.  It  also  turns  out that 200 CCM
             is  the  incorrect recommended  flow  as per  Al  Roddan  of
             Beckman.  We recommend  a  sample   flow  rate  of 160 CCM.
             This should  be  set with a calibrated rotameter.  Our  pres-
             sure setting turned out  to  be 4.35 PSIG on the  gauge.

         6.   This analyzer  also exhibits  seme  of the  same  problems as
             Teco 10A.

             a)  Noise  was  measured  up  to  an  average of 0.3%  of full
                 scale  peak  to peak,  sometimes  a  little higher.

             b)  Generally,  chemiluminescent analyzers  have  relatively
                 slow  response   in   comparison  to   other  emissions
                 analyzers primarily due  to sample  flew.   Even  though
                 it  is  about  3 seconds  faster  than  the Teco  10A the
                 951A would  still  slow down testing.  Response time for
                 analyzer alone from gas change at  inlet  port to  90% of
                 full  scale  is  6.3  seconds.   When  installed  in the
                 analytical  bench,  this  increased  to  11.4  seconds  as
                 compared to the Teco 10A  response of 14.8 seconds.

             c)  Similiar to the 10A there  are  sluggish  problems   after
                 a period of  non-use (2 to 3  days) for  the  first few
                 hours.  If  used continuously there  are less problems.

             d)  There   also  appears  to  be   some  sluggishness  when
                 returning  to  a  span  reading  after reading  a bag,
                 although this is  not serious.
VI.  DISCUSSION

     The Beckman  951A continuously analyzes  a  flowing  gas  sample and
     determines levels of nitric oxide (NO) or Oxides of  Nitrogen  (NOx)
                                  -5-

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(NO  +  N02  = NOx).   It utilizes  the chemi luminescent  method of:
detection.   To determine NO, sample NO is quantitatively  converted
into N02*  by oxidation with  molecular  ozone  produced  within  the
analyzer from air  or  oxygen  supplied  by  an  external  cylinder.
Approximately  10%  of  the  NOX  molecules  are  elevated  to  an
electronically  excited  state  accompanied  by  the  emission  of
photons.  These photons  strike  the photomultiplier detector,  gen-
erating a low level DC  current.  The current is  amplified to  drive
an output indicating  device,  (recorder  and/or  meter).  NOx deter-
mination is  identical  to that  described  above  except that, before
entry  into  the  reaction chamber,  the sample   is  routed through  a
converter where  the N02 component  is  converted  to NO.

After  receipt of  this  instrument  it was installed  in  a specifi-
cally designed checkout bench  for  preliminary  tests.   It was  then
installed  in  the  A001  exhaust   analytical   bench   as   shown in
Appendix D.   During these tests a number of problems  and  issues of
concern arose.

During initial checkout we found very poor  sensitivity and  occa-
sional  loss  of  zero.   It  was  found that  the  ozone  and  exhaust
lines  were  reversed  on  the  reaction   chamber  fittings.    This
apparently had  been  done  by  the  Beckman  service man.   We  also
found that the high voltage was 100 volts higher than nominal.  He
had  also raised  this to increase  sensitivity.   When we  corrected
the  reversal, the sensitivity problem was  corrected.  The higher
than necessary  voltage created  excessive dark  current.   When we
lowered the voltage to  nominal, this corrected the zero  (dark cur-
rent) problem.

We found that the recommended  sample pressure  of 4 PSIG  only  pro-
duced  138 CCM of   sample  capillary  flow  rather than  the  200 CCM
that the  manual   indicated.  After  additional  investigations  with
GM and  the Beckman  design  engineer, John Harman,  it was  finally
decided to  run  at the  160 CCM  flow rate that  was ttie  originally
recommended  value since no one  seemed  to know  where the  200 CCM
recommendation originated.   GM  is  running  at  the  160 CCM   rate
also.  We set this  flow from  a calibrated rotameter and marked it
on the pressure gauge.   It  reads approximately 4.35  PSIG.  Bypass
flow was set at  2  liters per minute.

It was  found  that after running a few converter efficiency checks
that the pressure matching method for NO  bypass flow balance  was
inadequate since   some readings were higher in the NO mode than the
NOx mode.  This was  corrected by using a  known N02  free cylinder
of NO  and  setting  the flow balance  until  the  readings were  the
same in both modes.

Initial  curve checks  on  the   instrument  on ranges  0-100 PPM  and
0-250 PPM were .less  than 1% non-linear.  Checks  on 0-50 PPM  were
-1.2%  non-linear  and  on 0-5000 PPM  were  6% non-linear.  However,
gases  on these   ranges  are  non-dependable  and  no  emphasis  was
placed on these checks.  However,  after installing the  instrument
                            -6-

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      in the analytical bench and during  a  series of converter tempera-
      ture adjustments  to  find  the  best converter  efficiency  it  was
      found that the higher temperature settings near the top end of the
      recommended range resulted  in  some abnormal curve plots, primarily
      on the 0-100 PPM range.  It was  really  never determined why these
      higher temperatures caused more  non-linearity on  that  one range.
      Possible  causes  could be  N0£  in the  cylinders  with  some unknown
      reaction   occurring  in the  converter.   This  same  phenomenon  was
      encountered in an EPA evaluation in March  1973 of a Ford modified
      Teco 10A  and is discussed  in excerpts  from that report in Appendix
      G.   These  problems  were  not  investigated  since time  did  not
      allow.   Since the higher temperatures  650° - 700°F not only caused
      this negative response but  affected the stability  to  some degree
      it was decided to run the converter on  the low end of recommended
      operation  (605°F)  that  would  give  98%+ converter  efficiency  and
      still result  in  acceptable  curve linearity.   It  should  be noted
      that each time the converter temperature was changed it was neces-
      sary to re-adjust the NO bypass balance.

      During our check out previous  to the actual comparison tests.  The
      converter heater blanket element opened.   The  Beckman service rep
      was contacted.   He  then brought out  a  new one and  it was installed
      and worked satisfactorily.

      A final converter efficiency of  98.1% was  accepted with a tempera-
      ture of  607°F.   Although  it was found  that 100% efficiency could
      be achieved at 691°F, 99%  at 689°F and 98.4 at 697°F that the low-
      er setting was more acceptable  for all-around operation.  More than
      sixteen settings  and efficiency checks were made  (See Appendix E).

      The bag comparison tests were  completed by the Light  Duty team  on
      actual certification  tests.   (Results  are on Appendix  B  and B~l.
      Although  the one to one comparisons of  all bags, sample and back-
      ground indicate a slight  bias  for the  951A to read  in the positive
      direction  (Mean  difference  of  +.33  PPM with  a standard deviation
      of 0.168),  the corrected samples (sample  minus background) corre-
      lated to a mean  difference of  +0.04 PPM with a standard deviation
      of  0.152.   All  readings were  on 0-100  PPM range.   The definite
      positive   bias  of the  951A  could not  be  explained.   However  the
      magnitude is so small that  it  is  not considered significant.

      C02  interference checks  were  made  by  C&M  personnel  with blended
      bags of  CC>2, NOx  and air.   (See  Appendix  C  tor  results.)   The
      different  results  of  the  two   tests can  be explained by  the fact
      that   the   interference   level   is  below   standard  instrument
      variability.
VII.  CONCLUSIONS/RECOMMENDATIONS

      A.  The Beckman 951A  is  an acceptable  instrument to measure  light
          duty vehicle NOx emissions.  It meets all EPA requirements  and
          Federal  Register  specifications.    However,  for   testing  on
                                  -7-

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           ranges  above  0-1000  PPM,  in  order  to  achieve  the  required
           linearity, different  combinations  of sample  and  ozone  capil-
           lary flow plus the use of oxygen for ozone  may have  to  be used.

           Since,  (a)  the  951A uses  the less  expensive and  safer  air
           rather  than  oxygen for  ozone,  (b)  it is  an atmospheric  type
           analyzer  thereby  eliminating  the  need for a  vacuum pump,  (c)
           it provides  a  slightly faster response than  the  10A,  (d)  its
           NOx emission measurement results correlate satisfactorily  with
           the  presently  used  Teco  10A,  (e)  its  configuration   and
           plumbing  requirements  are  compatible  with  our   analytical
           benches,  and  (f)  there is a  significant  amount  of  historical
           data available on these units from  other  laboratories,  it  is
           recommended as an equivalent,  if not  an  improved  alternative
           to the vacuum type NOx  analyzers  and could be used  to replace
           them in Light Duty Certification and E&D Light Duty  analytical
           benches.
VIII.  BIBLIOGRAPHY
       1.  Interferences in  Chemiluminescent  Measurement  of NO  and  N02
           Emissions from Combustion Systems,  R. Matthews, R. Sawyer,  and
           Robert Schefer,  Dept. of Mechanical Engineering,  University  of
           California,  Berkley,  Calif.  Nov.  1977.

       2.  Ford  Motor  Company  Intra-Company  Memo,  Atmospheric  Pressure
           Chemiluminescent  NOx  Analyzer,   R.  Ford  and   J.  Westveer,
           July 25, 1972.

       3.  Memo  from  Thermo-Electron  Corp  to  D.   Paulsell,  EPA,   NOx
           Converter Efficiency  Test  Expression,  John Dunlay, Sept.  17,
           1973.

       4.  Pressure Quenching in  the  Chemiluminescent Nitric Oxide-Ozone
           Reation, William Zolner,  Ph.D., Thermo-Electron  Corp.

       5.  EPA Inter-Office Memo, Report on NO/NOx Analyzer  Investigation
           Progress, S.D. Funk,  March  28,  1980.

       6.  Beckman Sales Literature, 1980.

       7.  EPA EOD  Engr. Staff  Project  Sub-Task Summary, Atmospheric  NOx
           Analyzer Evaluation,  S.D. Funk, Sept.  2,  1980.

       8.  Technical Report,  Evaluation of Philco-Ford  Chemiluminescent
           NOx Analyzer, June 1974.

       9.  Technical  Evaluation  of   Ford   Motor   Co.   Alternate  Test
           Equipment and Procedures, D.  Paulsell,  March 1973.
                                    -8-

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IX.  APPENDICES

     A.  Beckman 951A and 951 Schematic Flow Diagram.  A-l Beckman  951A
         and 951 Differences

     B.  NOx Exhaust  Sample  Bag Comparison  Table  B-l  Corrected  NOx
         Sample Comparisons
     C.   C0£ Interference Table 0^2  Graphs

     D.   Beckman 951A Plumbing Connections  in Analytical Bench

     E.   Converter Efficiency Graph

     F.   Excerpt from  an EPA  Technical  Evaluation  of a  Ford Modified
         Teco 10A.
                                 -9-

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1-25-81
APPENDIX A
                                                              Olc>nil«J Aif Of O«Y9-:A Icf


                                                              Chim'ilumin»«enl Itexiioi    Wimlvv.

                                                      	. O»-'->—-Les
                                                            /?  I      S,.n?l,

                                                      T-   I /I IJOM«J; Opiliir
                                                     now  LJ	^—p*^^;	"i
                                                     ftji.xxe T         «••»-'      I
                                                     Vj'.vt.—.  \.	      I  	T

                                                          ~x—"
                                             SAMPLE       •      N0/N0  M^


                                           B«k.P-c»u,.   BVPASS      ^"sol-ndd

                                             BrjuU.o/    Flowmew       ^
                                               FLOW DIAGRAM OF BECKMAN 951A
                                                                                       .SL,S    I	ij-s-m f^v..-'=i
                                       FLOW  DIAGRAM  OF  BECKMAN 951

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1-25-81                                                           APPENDIX A-l
                     Differences in Beckman 951A and 951

            In the Beckman 951A:

                1.  A type J thermocouple output of converter temperature
                    is provided.

                2.  Pressure settings and flows are visible thru the new
                    front panel window.

                3.  Trim pots to separately trim each range have been added.

                4.  The span and zero solenoids are removed.

                5.  An led indicator showing converter cycling has
                    been added.

                6.  Converter temperature adjust is now from front panel.

                7.  Improved flow balancing thru use of needle valve.
                    The use of a needle valve has improved flow balancing.

                8.  Internal ozonator on/off switch has been added.

                9.  Internal changes of flow configuration and pressure
                    regulation have been made.

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1-25-81
            APPENDIX E
                                                 NOx EXHAUST SAMPLE BAG COMPARISONS
                                                         Diff. = 951A - 10A
BECKMAN VS. TECO
READINGS = PPM
DATE
11-20-80
11-20-80
11-20-80
11-20-80
11-21-80
11-21-80
] 1-21-80
11-21-80
11-20-80
11-20-80
11-21-80
11-21-80
TEST #
80-6816
80-6823
80-6819
80-6820
80-6825
80-6833
80-6830
80-6828
80-6824
80-6864
80-6869
80-6865
BAG 1 and 4
BG
95 1A 10A
0.7 0.6
0.7 0.2
0.6 0.1
0.8 0.3
0.6 0.1
0.7 0.1
0.5 0.2
0.5 0.2
0.6 0.1
0.4 0.2
0.7 0.2
0.7 0.2
DIFF
+0.1
+0.5
+0.5
+0.5
+0.5
+0.6
+0.3
+0.3
SAMP
951 A 10A
27.9 27.9
60.3 60.3
2.5 2.2
21.9 21.6
22.0 21.6
13.5 13.3
16.5 16.3
14.7 14.4
+0.5 80.8 80.1
+0.2
-+0.5
+0.5
26.4 26.2
41.7 41.4
2.3 1.8

DIFF
0.0
0.0
+ 0.3
+0.3
+0.4
+0.2
BAG 2
BG
951A 10A
0.8 0.2
0.6 0.1

0.7 0.3
0.6 0.1
0.5 0.0
+0.2_[0.5 0.2
+0.3
+0.7
+0.2
+0.3
+0.5
0.5 0.2

0.4 0.2
0.4 0.2
0.5 0.3
DIFF^
+0.6
+0.5

+0.4
+ 0.5
+0.5
+0.3
+0.3

+0.2
+0.2
+0.2
and 5 BAG 3 and 6
SAMP
951A 10A
9.7 9.1
13.8 13.1

7.1 6.7
4.3 3.8
5.1 4.6
7.1 6.8
4.1 3.7

; 8.5 8.4
10.3 9.9
0.8 0.6
DIFF
+0.6
+0.7

+0.4
+0.5
+0.5
+0.3
+0.4

+0.1
+0.4
+0.2
BG
951A 10A
0.3 0.1
0.3 0.0

0.7 0.3
0.3 0.0
0.3 0.0
0.3 0.1
0.3 0.1

0.2 0.1
0.4 0.2
0.6 0.3
DIFF
+0.2
+0.3

+0.4
+0.3
+0.3
+0.2
+0.2

+0.1
+0.1
+0.3
SAMP
951A 10A
19.5 19.1
43.7 43.6

11.3 10.9
12.4 12.1
11.6 11.3
17.9 17.8
5.7 5.6

12.. 9 12.8
18.1 17.9
2.1 1.9


DIFF
+0.4
+0.1

+0.4
+0.3
+0.3
+0.1
+0.1

I
+0.1
l
+0.2
i
+0.2

                                                                                             MEAN DIFFERENCE +0.33 PPM or
                                                                                                               0.33% of
                                                                                             FULL SCALE ON 0-100 PPM RANGE
                                                                                             STD DEV.           0.168

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1-29-81
                                                                                                        APPENDIX  B-l
DATE
TEST #
     CORRECTED NOx SAMPLE COMPARISONS
95]A (SAMP.  - BG) - 10A (SAMP -BG)
    CORRECTED SAMPLES

11-20-80
11-20-80
11-20-80
11-20-80
11-21-80
11-21-80
11-21-80
11-21-80
11-20-80
11-20-80
11-21-80
11-21-80

80-6816
80-68>23
80-6819
80-6820
BAG 1-4
TRANS COLD
951A 10A
27.2 27.3
59.6 60.1
1.9 2.1
21.1 21.3
1
80-6825 J21.4 21.5
80-6833
80-6830
80-6828
80-6824
80-6864
80-6869
80-6865
12.8 13.2
16.0 16.1
14.2 14.2
80.2 80.1
20.2 26.0
41.0 41.2
1.6 1.6
DIFF
-0.1
-0.5
-0.2
-0.2
+0.1
-0.4
-0.1
0.0
+0.1
0.0
-0.1
0.0
BAG 2-5
STABLE COLD
951A 10A
8.9 8.9
13.2 13.0

6.4 6.4
3.7 3.7
4.6 4.6
6.6 6.6
3.6 3.5

8.1 8.2
9.9 9.7
-0.3 -0.3
DIFF
0.0
+0.2

0.0
0.0
0.0
0.0
+0.1

-0.1
+0.2
0.0
BAG 3-6
TRANS. HOT
95^A lOA
19.2 19.0
43.4 43.6

10.6 10.6
12.1 12.1
11.3 11.3
17.6 17.8
5.4 5.5

12.7 12.7
17.7 17.7
1.5 1.6
DIFF
+0.2
-0.2

0.0
0.0
0.0
-0.2
-0.1

0.0
0.0
-0.1

READINGS = PPM
                       MEAN DIFF -0.12
                       STD DEV.    .18
                                    MEAN DIFF +.04
                                    STD. DEV   .10
                           MEAN DIFF.
                           STD. DEV.
-0.04
 0.11
 TOTAL TESTS
MEAN DIFF =-0.043 PPM
STD DEV   = 0.152

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                                                                       APPENDIX C
                                  C02  INTERFERENCE


                     (NOx ANALYZERS BECKMAN 951A vs. TECO IDA)
RANGE  0-100PPM



BAG 1
2
3
4
5
6
7
8
CALC.
BLEND '
PPM NOx CO 2%

52.3 0
52.3 1.5
52.3 2.5
52.3 4.81
52.3 0
52.3 1.5
52.3 2.51
52.3 4.81

C02%

0
1.47
. 2.45
4.77
0
1.45
2.47
. 4.77
MEASURED
PPM
NOx
95 1A 10A
51.6 50.8
51.9 51.2
49.6 49.5
51.1 50.8
51.1 50.2
51.2 50.5
30.9 50.2
51.3 50.7

NO
951A 10A
41.9 40.9
41.2 40.4
34.0 33.9
38.9 38.6
41.6 41.3
40.7 40.6
40.2 39.9
41.3 41.0
OFFSET
951A-10A
NOx NO

+0.8 +1.0
+0.7 +0.8
+0.1 +0.1
+0.3 +0.3
+0.9 +0.3
+0.7 +0.1
+0.7 +0.3
+0.6 +0.3
BIAS
@ 0% C02
951A-10A
NOx NO

+0.8 +1.0

!
i
1
+0.9 +0.3
5
J
I
t
\
INTERFERENCE
OFFSET - BIAS
NOx NO

0 0
-0.1 -0.2
-0.7 -0.9
-0.5 -0.7
0 0
-0.2 -0.2
-0.2 0.0
-0.3 0.0
NOTE:  Bias  is  defined as the  difference  between the 951A  and  the 10A readings at  0%  C02-   10A
is considered with no interference.

         Offset  is defined as  the difference between  the  951A and the 10A with  interference and
         bias combined.

         Interference is calculated by  subtracting the bias from  the  offset  at  various  levels of
         C02.

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APPENDIX C-l
1-25-81

-------
APPENDIX C-2
1-25-81

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TO ATMOSPHERE
                         NOTE.:
 I. VACUUM
 2.
   FL-OOR
.3.. ENCLOSURE  DENOTED  AS
                                                P2. L-OOATSTO l/Sj E>C
                           .•£
                                        CTYR

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APPENDIX E

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V
   1  25 81
                                                  APPENDIX F
the back pressure with precision during the measurement
period.

     The converter temperature and flow were studied to
assess their affect on measured values.  A valve is posi-
tioned in the bypass line of the converter to simulate the
pressure drop of the converter and thus achieve balanced
flows and resultant equivalent readings as per above dis-
cussion.  See Fig. 1C.
     One perplexing characteristic concerning the converter
v/as the lower values obtained for the span gas in the con-
vert mode than in the bypass mode.  Initially it was thought
to be a flow unbalance, but tests showed increeised loss of
NO reading as the converter temperature increases.  There
are a series of reactions which may occur to produce this
effect :
     a)  2N02 ~~
                       °2
     b)  O2 + 2C — - 2CO

     c)  2NO + 2CO — »- N2
                           2CO2
Reaction  (c) requires a reducing atmosphere and  is enhanced
in the +400°C temperature range.  In the case of bag  analy-
sis from CVS, the absence of the reducing atmosphere  makes
this reaction unlikely.  These reactions are speculative r
but theoretically could cause the effects; however, opera-
tion at the recommended temperature of  475°C produces neg-
ligible losses as well as high conversion efficiency.   See
Fig. ID.
     E.  Several miscellaneous  aspects of 'operation  are
mentioned here as areas of possible  improvement.   In this
particular instrument, the sample pump bypass  valve,  N2,
was teed to the sample pressure regulator bleed  off  tube,
both connected to the exhaust fan.   The  influence  of the
pump backflow on the regulator  changed a span  val^te  from
90.7 to 88.5, or -2.5%.  This effect simply  reflects a
change in sample flow.  The bypass,  bleed off, and reaction
chamber exhaust should all be independently  vented to the
exhaust fan.  See Fig. 1C.

     A gage to monitor the sample capillary  back pressure
to ± .5'!H20 and a finer control metering valve should be
installed in the sample line  to assure flow  equivalence
during all measurements.

-------