SOUTH COAST QUALITY MANAGEMENT DISTRICT

METHOD 3.1

GAS ANALYSIS FOR DRY MOLECULAR WEIGHT AND EXCESS AIR

OFFICE OF OPERATIONS
TECHNICAL SERVICES DIVISION
MARCH 1989
 METHOD 3.1

GAS ANALYSIS FOR DRY MOLECULAR WEIGHT AND EXCESS AIR

TABLE OF CONTENTS

Section

1. Overview

1.1 Principle

1.2 Applicability

2. Field Procedure

2.1 Apparatus

2.2 Dry Molecular Weight Determination

2.3 Emission Rate Correction Factor, Excess Air

Determination, or Dry Molecular Weight

Determination

2.4 Leak Check Procedures for Orsat Analyzers

3. Engineering Calculations and Reporting

3.1 Nomenclature

3.2 Percent Excess Air

3.3 Dry Molecular Weight

 METHOD 3.1

GAS ANALYSIS FOR DRY MOLECULAR WEIGHT AND EXCESS AIR

Section 1 of 3

1. Overview

1.1 Principle

A gas sample is extracted from a stack by single-

point grab sampling, single-point integrated

sampling, or multi-point integrated sampling.

The sample is analyzed for percent carbon dioxide

(CO2), percent oxygen (O2), and, if necessary,

percent carbon monoxide (CO). An Orsat analyzer

or other analyzer specified in Method 10.1 may be

used. Method 10.1 is an alternative method

requiring laboratory analysis.

1.2 Applicability

This method determines CO2 and O2 concentrations,

excess air from fossil fuel combustion sources,

and dry molecular weight of a sample from a gas

stream consisting primarily of CO2, O2, CO, and

nitrogen (N2).

3.1-1
Other methods, as well as modifications to this

procedure, may apply for some or all of the above

determinations. Specific methods and

modifications include:

a. A multi-point sampling method using an Orsat

analyzer to analyze individual grab samples

obtained at each point.

b. Methods 10.1 or 100.1.

c. A method using CO2 or O2 and stoichiometric

calculations to determine dry molecular

weight and excess air.

d. Assigning a value of 29.0 for dry molecular

weight, in lieu of actual measurements, for

processes burning natural gas, coal, or oil.

These methods and modifications may be subject to

the approval of the Executive Officer.

3.1-2
 METHOD 3.1

GAS ANALYSIS FOR DRY MOLECULAR WEIGHT AND EXCESS AIR

Section 2 of 3

2. Field Procedures

2.1 Apparatus

As alternatives to the sampling apparatus and

systems described here, other sampling systems

(e.g. liquid displacement) may be used provided

they are capable of obtaining a representative

sample, maintaining a constant sampling rate, and

are otherwise capable of yielding acceptable

results. Use of such systems is subject to the

approval of the Executive Officer.

2.1.1 Grab Sampling

Refer to Figure 3.1-1.

3.1-3
 a. Probe

The probe should be made of

stainless steel or borosilicate

glass tubing, equipped with an in-

stack or out-of-stack filter to

remove particulate matter. (A plug

of glass wool is satisfactory for

this purpose.) Any other material

inert to O2, CO2, CO, and N2 and

resistant to temperature at

sampling conditions may be used for

the probe.

b. Pump

Use a one-way squeeze bulb, or

equivalent, to transport the sample

to the analyzer or evacuated flask.

2.1.2 Integrated Sampling

Refer to Figure 3.1-2.

3.1-4
a. Probe

Options described above for the

grab sampling probe are suitable.

b. Condenser

An air-cooled or water-cooled

condenser, or other condenser that

will not remove O2, CO2, CO,and N2,

may be used to remove excess

moisture which would interfere with

the operation of the pump and flow

meter.

c. Valve

Use a needle valve to adjust sample

gas flow rate.

d. Pump

A leak-free peristaltic pump, or

equivalent, transports sample gas

to the flexible bag. Install a

small surge tank between the pump

3.1-5
 and rate meter to eliminate the

pulsation effect of a diaphragm

pump on the rotameter, if used.

e. Rate Meter

The rotameter,or equivalent rate

meter used, should be capable of

measuring flow rate to within + 5

percent of the selected flow rate.

A flow rate range of 500 to 1000

cm3/min is suggested. The

rotameter is not needed if a speed

control is used on the pump.

f. Flexible Bag

Use any leak-free bag made with

plastic (e.g. Tedlar, Mylar,

Teflon) or plastic-coated aluminum

(e.g. aluminized Mylar) film, or

equivalent, having a capacity

consistent with the selected flow

rate and time interval for the test

run. The suggested capacity is in

the range of 15 to 90 liters.

3.1-6
 To leak check the bag, connect it

to a water manometer and pressurize

the bag to 5 to 10 cm H2O (2 to 4

in. H2O) and allow to stand

overnight. A deflated bag

indicates a leak.

g. Pressure Gauge

A water-filled U-tube manometer, or

equivalent, of about 30 cm (12 in.)

is used for the flexible bag leak

check.

h. Vacuum Gauge

A mercury manometer, or equivalent,

of at least 760 mm (30 in.) Hg is

used for the sampling train leak-

check.

2.1.3 Orsat Analyzer

An Orsat analyzer may be used for on-

site analysis. For Orsat analyzer

maintenance and operation procedures,

3.1-7
 follow manufacturer's instructions

unless otherwise specified herein.

Appropriate leak-free sample containers

(two-liter glass or stainless steel

flasks, or Tedlar bags) may be used to

store samples for later laboratory

analysis. Method 100.1 may be used for

on-site continuous monitoring.

2.2 Dry Molecular Weight Determination

Use one of the three sampling and analytical

procedures described below to determine dry

molecular weight.

2.2.1 Single-Point Grab Sampling and

Analytical Procedure

The sampling point in the duct should

either be at the centroid of the cross

section or at a point no closer to the

walls than 1.00 m (3.3 ft), unless

otherwise specified by the Executive

Officer.

3.1-8
Set up equipment as shown in Figure

3.1-1, making sure all connections ahead

of the analyzer are tight and leak-free.

If an Orsat analyzer is used, the

analyzer should be leak checked by

following the procedure in Section 2.4.

Place the probe in the stack with the

tip of the probe positioned at the

sampling line. Purge the sampling line.

Draw a sample into the analyzer and

immediately analyze it for percent CO2

and percent O2.

Determine the percentage of the gas that

is N2 and CO by subtracting the sum of

the percent CO2 and percent O2 from 100

percent.

Calculate the dry molecular weight as

outlined in Section 3.3.

Repeat sampling, analysis, and

calculation procedures

until the dry molecular weights of any

three grab samples differ from their

3.1-9
 mean by no more than 0.3 g/g-mole (0.3

lb/lb-mole).

Report this mean value to the nearest

0.1 g/g-mole (0.1 lb/lb-mole).

2.2.2 Single-Point Integrated Sampling and

Analytical Procedure

Locate the sampling point in the duct as

specified in Section 2.2.1.

Leak check the flexible bag as in

Section 2.1.2 (f). Set up equipment as

shown in Figure 3.1-3. Just prior to

sampling, leak check the train by

placing a vacuum gauge at the probe

inlet, pulling a vacuum of at least 250

mm (10 in.) Hg, plugging the outlet at

the bag inlet, and then turning off the

pump. The vacuum should remain stable

for at least 30 seconds.

Evacuate the flexible bag.

Connect the probe and place it in the

stack, with the tip of the probe

3.1-10
positioned at the sampling point. Purge

the sampling line. Connect the bag and

make sure that all connections are tight

and leak-free.

Sample at a constant rate throughout the

total time of the pollutant emission

rate determination, or as specified by

the Executive Officer. Collection of at

least 15 liters (0.5 ft3) of sample gas

is recommended.

Obtain one integrated flue gas sample

during each pollutant emission rate

determination.

Within 24 hours after the sample is

taken, analyze it for percent CO2 and

percent O2 using either an Orsat

analyzer, Method 100.1, or Method 10.1.

If an Orsat analyzer is used, an

optional Orsat leak check (described in

Section 2.4) may be performed before

this determination. Determine the

percentage of the gas that is N2 and CO

by subtracting the sum of percent CO2

and percent O2 from 100 percent.

3.1-11
 Calculate the dry molecular weight as

indicated in Section 3.3.

Repeat analysis and calculation

procedures until the individual dry

molecular weights for any three analyses

differ from their mean by no more than

0.3 g/g-mole (0.3 lb/lb-mole).

Report this mean value to the nearest

0.1 g/g-mole (0.1 lb/lb-mole).

2.2.3 Multi-Point Integrated Sampling

and Analytical Procedure

Unless otherwise specified by the

Executive Officer, use a minimum of

eight traverse points for circular

stacks with diameters less than

61 cm (24 in.), a minimum of nine points

for rectangular stacks with equivalent

diameters less than 61 cm (24 in.), and

a minimum of twelve points for all other

cases. Traverse points should be

located according to Method 1.1. The

use of fewer points is subject to

approval of the Executive Officer.

3.1-12
 Follow the procedures outlined in

Section 2.2.2. but traverse all sampling

points and sample at each point for an

equal length of time. Record sampling

data as shown in Figure 3.1-3.

2.3 Emission Rate Correction Factor, Excess Air

Determination, or Dry Molecular Weight

Determination

2.3.1 Single-Point Grab Sampling and

Analytical Procedure

See Section 2.2.1.

If an excess air determination is

desired, proceed as follows:

a. Immediately analyze the sample as

in Sections 2.2.2. for percent

CO2, O2, and CO.

3.1-13
b. Determine the percentage of the gas

that is N2 by subtracting the sum

of the percent CO2, percent O2, and

percent CO from 100 percent.

c. Calculate percent excess air as

outlined in Section 3.2.

To ensure complete absorption of the

CO2, O2, or if applicable, CO, make

repeated passes through each absorbing

solution until two consecutive readings

are the same.

Several passes (three or four) should be

made between readings. (If constant

readings cannot be obtained after three

consecutive readings, replace the

absorbing solution.)

After the analysis is completed, leak

check (mandatory) the Orsat analyzer

once again, as described in Section 2.4.

Results will be valid only if the Orsat

analyzer passes this leak test before

and after the analysis.

3.1-14
 Note: Since this single-point grab

sampling and analytical procedure is

normally conducted in conjunction with a

single-point grab sampling and

analytical procedure for a pollutant,

only one analysis is ordinarily

conducted. Therefore, great care must

be taken to obtain a valid sample and

analysis. Although in most cases only

CO2 or O2 is required, it is recommended

that both CO2 and O2 be measured and the

stoichiometric relation be used to

validate the analytical data.

2.3.2 Single-Point Integrated Sampling and

Analytical Procedure

See Section 2.2.2.

If an excess air determination is

desired, proceed as follows:

a. Within 24 hour after the sample is

taken, analyze it for percent CO2,

O2, and CO.

3.1-15
b. Determine the percentage of the gas

that is N2 by subtracting the sum

of the percent CO2, percent O2, and

percent CO from 100 percent.

c. Calculate percent excess air as

outlined in Section 3.2.

To ensure complete absorption of the

CO2, O2, or if applicable, CO, make

repeated passes through each absorbing

solution until two consecutive readings

are the same. Make three or four passes

between readings. (If constant readings

cannot be obtained after three

consecutive readings, replace the

absorbing solution.)

Repeat the analysis until the following

criteria are met:

For percent CO2, repeat the analytical

procedure until the results of any three

analyses differ by no more than (1) 0.3

percent by volume when CO2 is greater

than 4.0 percent, or (2) 0.2 percent by

volume when CO2 is less than or equal to

3.1-16
 4.0 percent. Average the three

acceptable values of percent CO2 and

report the results to the nearest 0.1

percent.

After the analysis is completed, leak

check (mandatory) the Orsat analyzer

again, as described in Section 2.4.

Results will be valid only if the Orsat

analyzer passes this leak test before

and after the analysis.

Note: Although in most instances only

CO2 or O2 is required, it is recommended

that both CO2 and O2 be measured and

the stoichiometric relation be used to

validate the analytical data.

2.3.3 Multi-Point Integrated Sampling and

Analytical Procedure

Both the minimum number of sampling

points and the sampling point location

are specified in Section 2.2.3. The use

of fewer points than specified is

subject to the approval of the Executive

Officer.

3.1-17
 Follow the procedures outlined in

Section 2.2.2 for sample collection.

2.4 Leak Check Procedure for Orsat Analyzers

Since moving an Orsat analyzer frequently causes

it to leak, an analyzer should be thoroughly leak

checked on-site before the flue gas sample is

introduced into it.

Bring the liquid level in each pipet up to the

reference mark on the capillary tubing and then

close the pipet stopcock. Raise the leveling bulb

sufficently to bring confining liquid meniscus

onto the graduated portion of the buret and then

close the manifold stopcock. Record the meniscus

position. Observe the meniscus in the buret and

the liquid level in the pipet for movement over

the next 4 minutes. For the Orsat analyzer to

pass the leak check, two conditions must be met:

· The liquid level in each pipet must not fall

below the bottom of the capillary tubing

during this 4-minute interval.

3.1-18
· The meniscus in the buret must not change by

more than 0.2 ml during this 4-minute

interval.

If the analyzer fails the leak check procedure,

check all rubber connections and stopcocks until

the cause of the leak is identified.

Disassemble, clean, and regrease leaking

stopcocks. Replace leaking rubber connections.

Reassemble the analyzer and repeat the leak check

procedure.

3.1-19
 METHOD 3.1

GAS ANALYSIS FOR DRY MOLECULAR WEIGHT AND EXCESS AIR

Section 3 of 3

3. Calculations

Perform calculations and record values to at least one

decimal place more than that of the acquired data.

Round off the final results.

3.1 Nomenclature

Md = Dry molecular weight, g/g-mole

(lb/lb-mole)

Percent EA = Percent excess air

Percent CO2 = Percent CO2 by volume (dry basis)

Percent O2 = Percent O2 by volume (dry basis)

Percent CO = Percent CO by volume (dry basis)

Percent N2 = Percent N2 by volume (dry basis)

0.264 = Ratio of O2 to N2 in air, v/v

0.280 = Molecular weight of N2 or CO,

divided by 100

0.320 = Molecular weight of O2 divided by

100

3.1-20
 0.440 = Molecular weight of CO2 divided by

100

3.2 Percent Excess Air

Calculate the percent excess air (if applicable)

by substituting the appropriate values of percent

O2, CO, and N2 (obtained from Section 2.3.1 or

2.3.2) in the following equation:

Percent O2-0.5 Percent CO

Percent EA = x 100
0.264 Percent N2-(Percent O2-0.5 Percent CO)

This equation assumes that ambient air is used

as the source of O2 and that the fuel does not

contain appreciable amounts of N2 (as does coke

or blast furnace gas). For cases where

appreciable amounts of N2 are present (coal, oil,

and natural gas do not contain appreciable

amounts of N2) or when oxygen enrichment is used,

alternate methods are required, subject to

approval of the Executive Officer.

3.1-21
3.3 Dry Molecular Weight

Use the following equation to calculate the dry

molecular weight of the stack gas:

Md = 0.440 (percent CO2) + 0.320 (percent

O2) + 0.280 (percent N2 + percent

CO)

Note: The above equation does not consider the

argon present in air (about 0.9 percent,

molecular weight of 37.7) which introduces a

negative error of about 0.4 percent. The tester

may opt to include argon in the analysis using

procedures approved by the Executive Officer.

3.1-22