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ANALYSIS OF FLUE

GASES
The object of a flue gas analysis is the determination of the
completeness of the combustion of the carbon in the fuel,
and the amount and distribution of the heat losses due to
incomplete combustion. The quantities actually determined
by an analysis are the relative proportions by volume, of
carbon dioxide (CO2), oxygen (O), and carbon monoxide
(CO), the determinations being made in this order.
The variations of the percentages of these gases in an
analysis is best illustrated in the consideration of the
complete combustion of pure carbon, a pound of which
requires 2.67 pounds of oxygen or 32 cubic feet at 60 degrees
Fahrenheit. The gaseous product of such combustion will
occupy, when cooled, the same volume as the oxygen,
namely, 32 cubic feet. The air supplied for the combustion is
made up of 20.91 per cent oxygen and 79.09 per cent
nitrogen by volume. The carbon united with the oxygen in
the form of carbon dioxide will have the same volume as the
oxygen in the air originally supplied. The volume of the
nitrogen when cooled will be the same as in the air supplied,
as it undergoes no change. Hence for complete combustion of
one pound of carbon, where no excess of air is supplied, an
analysis of the products of combustion will show the
following percentages by volume:
Actual
Volume Per
for One Cent
Pound by
Carbon Volume
Cubic Feet
Carbon Dioxide 32 = 20.91
Oxygen 0 = 0.00
Nitrogen 121 = 79.09

Air required for one pound
153 =100.00
Carbon
For 50 per cent excess air the volume will be as follows:
153 1 = 229.5 cubic feet of air per pound of carbon.
Actual Volume
for One Per Cent
Pound Carbon by Volume
Cubic Feet
Carbon Dioxide 32 = 13.91 20.91
}= per
Oxygen 16 = 7.00
cent
Nitrogen 181.5 = 79.09



Air required for one 229.5 =100.00
pound Carbon
For 100 per cent excess air the volume will be as follows:
153 2 = 306 cubic feet of air per pound of carbon.

Actual
Volume
for One Per Cent
Pound by Volume
Carbon
Cubic Feet
Carbon Dioxide 32 = 10.45 20.91
}=
Oxygen 32 = 10.45 per cent
Nitrogen 242 = 79.09



Air required for one
306 =100.00
pound Carbon
In each case the volume of oxygen which combines with the
carbon is equal to (cubic feet of air 20.91 per cent)32
cubic feet.

It will be seen that no matter what the excess of air supplied,


the actual amount of carbon dioxide per pound of carbon
remains the same, while the percentage by volume decreases
as the excess of air increases. The actual volume of oxygen
and the percentage by volume increases with the excess of
air, and the percentage of oxygen is, therefore, an indication
of the amount of excess air. In each case the sum of the
percentages of CO2 and O is the same, 20.9. Although the
volume of nitrogen increases with the excess of air, its
percentage by volume remains the same as it undergoes no
change while combustion takes place; its percentage for any
amount of air excess, therefore, will be the same after
combustion as before, if cooled to the same temperature. It
must be borne in mind that the above conditions hold only
for the perfect combustion of a pound of pure carbon.
Carbon monoxide (CO) produced by the imperfect
combustion of carbon, will occupy twice the volume of the
oxygen entering into its composition and will increase the
volume of the flue gases over that of the air supplied for
combustion in the proportion of

100 + the per cent CO

When pure carbon is the fuel, the sum of the percentages by


volume of carbon dioxide, oxygen and one-half of the carbon
monoxide, must be in the same ratio to the nitrogen in the
flue gases as is the oxygen to the nitrogen in the air supplied,
that is, 20.91 to 79.09. When burning coal, however, the
percentage of nitrogen is obtained by subtracting the sum of
the percentages by volume of the other gases from 100. Thus
if an analysis shows 12.5 per cent CO2, 6.5 per cent O, and
0.6 per cent CO, the percentage of nitrogen which ordinarily
is the only other constituent of the gas which need be
considered, is found as follows:
100 - (12.5 + 6.5 + 0.6) = 80.4 per cent.
The action of the hydrogen in the volatile constituents of the
fuel is to increase the apparent percentage of the nitrogen in
the flue gases. This is due to the fact that the water vapor
formed by the combustion of the hydrogen will condense at a
temperature at which the analysis is made, while the
nitrogen which accompanied the oxygen with which the
hydrogen originally combined maintains its gaseous form
and passes into the sampling apparatus with the other gases.
For this reason coals containing high percentages of volatile
matter will produce a larger quantity of water vapor, and
thus increase the apparent percentage of nitrogen.
Air Required and SuppliedWhen the ultimate analysis of a
fuel is known, the air required for complete combustion with
no excess can be found as shown in the chapter on
combustion, or from the following approximate formula:
Pounds
of air C O S
required 34.5
= ( + (H - )+ )[29] (11)
per 6
pound of 3 8 8
fuel
where C, H and O equal the percentage by weight of carbon,
hydrogen and oxygen in the fuel divided by 100.
[Pg 157]
When the flue gas analysis is known, the total, amount of air
supplied is:
Pounds of N
air
3.03 [30 (12
supplied = ( )C
6 ] )
per pound
of fuel CO2 + CO

where N, CO2 and CO are the percentages by volume of


nitrogen, carbon dioxide and carbon monoxide in the flue
gases, and C the percentage by weight of carbon which is
burned from the fuel and passes up the stack as flue gas.
This percentage of C which is burned must be distinguished
from the percentage of C as found by an ultimate analysis of
the fuel. To find the percentage of C which is burned, deduct
from the total percentage of carbon as found in the ultimate
analysis, the percentage of unconsumed carbon found in the
ash. This latter quantity is the difference between the
percentage of ash found by an analysis and that as
determined by a boiler test. It is usually assumed that the
entire combustible element in the ash is carbon, which
assumption is practically correct. Thus if the ash in a boiler
test were 16 per cent and by an analysis contained 25 per
cent of carbon, the percentage of unconsumed carbon would
be 16 .25 = 4 per cent of the total coal burned. If the coal
contained by ultimate analysis 80 per cent of carbon the
percentage burned, and of which the products of combustion
pass up the chimney would be 80 - 4 = 76 per cent, which is
the correct figure to use in calculating the total amount of air
supplied by formula (12).
The weight of flue gases resulting from the combustion of a
pound of dry coal will be the sum of the weights of the air
per pound of coal and the combustible per pound of coal, the
latter being equal to one minus the percentage of ash as
found in the boiler test. The weight of flue gases per pound
of dry fuel may, however, be computed directly from the
analyses, as shown later, and the direct computation is that
ordinarily used.
The ratio of the air actually supplied per pound of fuel to
that theoretically required to burn it is:

N
3.036 ( ) C
CO2 + CO
(1
3)
C O
34.56 ( + H - )
3 8

in which the letters have the same significance as in formulae


(11) and (12).
The ratio of the air supplied per pound of combustible to the
amount theoretically required is:

N
(14)
N - 3.782(O - CO)

which is derived as follows:


The N in the flue gas is the content of nitrogen in the whole
amount of air supplied. The oxygen in the flue gas is that
contained in the air supplied and which was not utilized in
combustion. This oxygen was accompanied by 3.782 times its
volume of nitrogen. The total amount of excess oxygen in the
flue gases is (O - CO); hence N - 3.782(O - CO)
represents the nitrogen content in the air actually required
for combustion and N (N - 3.782[O - CO]) is the [Pg 158]
ratio of the air supplied to that required. This ratio minus
one will be the proportion of excess air.
The heat lost in the flue gases is L = 0.24 W (T - t) (15)

Where L= B. t. u. lost per pound of fuel,


weight of flue gases in pounds per pound of dry
W=
coal,
T= temperature of flue gases,
t = temperature of atmosphere,
0.24= specific heat of the flue gases.
The weight of flue gases, W, per pound of carbon can be
computed directly from the flue gas analysis from the
formula:

11 CO2 + 8 O + 7 (CO + N)
(16
)
3 (CO2 + CO)
where CO2, O, CO, and N are the percentages by volume as
determined by the flue gas analysis of carbon dioxide,
oxygen, carbon monoxide and nitrogen.
The weight of flue gas per pound of dry coal will be the
weight determined by this formula multiplied by the
percentage of carbon in the coal from an ultimate analysis.
Fig. 20. Loss Due to Heat Carried Away by Chimney Gases
for Varying Percentages of Carbon Dioxide.
Based on Boiler Room Temperature = 80 Degrees
Fahrenheit.
Nitrogen in Flue Gas = 80.5 Per Cent. Carbon Monoxide in
Flue Gas = 0. Per Cent
Fig. 20 represents graphically the loss due to heat carried
away by dry chimney gases for varying percentages of CO2,
and different temperatures of exit gases.

The heat lost, due to the fact that the carbon in the fuel is not
completely burned and carbon monoxide is present in the
flue gases, in B. t. u. per pound of fuel burned is:

CO
L' = 10,150 ( ) (17)
CO + CO2

where, as before, CO and CO2 are the percentages by volume


in the flue gases and C is the proportion by weight of carbon
which is burned and passes up the stack.
Fig. 21 represents graphically the loss due to such carbon in
the fuel as is not completely burned but escapes up the stack
in the form of carbon monoxide.
Fig. 21. Loss Due to Unconsumed Carbon Contained in the
CO in the Flue Gases
Apparatus for Flue Gas AnalysisThe Orsat apparatus,
illustrated in Fig. 22, is generally used for analyzing flue
gases. The burette A is graduated in cubic centimeters up to
100, and is surrounded by a water jacket to prevent any
change in temperature from affecting the density of the gas
being analyzed.
For accurate work it is advisable to use four pipettes, B, C,
D, E, the first containing a solution of caustic potash for the
absorption of carbon dioxide, the second an alkaline solution
of pyrogallol for the absorption of oxygen, and the remaining
two an acid solution of cuprous chloride for absorbing the
carbon monoxide. Each pipette contains a number of glass
tubes, to which some of the solution clings, thus facilitating
[Pg 160] the absorption of the gas. In the pipettes D and E,
copper wire is placed in these tubes to re-energize the
solution as it becomes weakened. The rear half of each
pipette is fitted with a rubber bag, one of which is shown at
K, to protect the solution from the action of the air. The
solution in each pipette should be drawn up to the mark on
the capillary tube.

Fig. 22. Orsat Apparatus


The gas is drawn into the burette through the U-tube H,
which is filled with spun glass, or similar material, to clean
the gas. To discharge any air or gas in the apparatus, the
cock G is opened to the air and the bottle F is raised until the
water in the burette reaches the 100 cubic centimeters mark.
The cock G is then turned so as to close the air opening and
allow gas to be drawn through H, the bottle F being lowered
for this purpose. The gas is drawn into the burette to a point
below the zero mark, the cock G then being opened to the air
and the excess gas expelled until the level of the water in F
and in A are at the zero mark. This operation is necessary in
order to obtain the zero reading at atmospheric pressure.
The apparatus should be carefully tested for leakage as well
as all connections leading thereto. Simple tests can be made;
for example: If after the cock G is closed, the bottle F is
placed on top of the frame for a short time and again
brought to the zero mark, the level of the water in A is above
the zero mark, a leak is indicated.
Before taking a final sample for analysis, the burette A
should be filled with gas and emptied once or twice, to make
sure that all the apparatus is filled with the new gas. The
cock G is then closed and the cock I in the pipette B is
opened and the gas driven over into B by raising the bottle
F. The gas is drawn back into A by lowering F and when the
solution in B has reached the mark in the capillary tube, the
cock I is closed and a reading is taken on the burette, the
level of the water in the bottle F being brought to the same
level as the water in A. The operation is repeated until a
constant reading is obtained, the number of cubic
centimeters being the percentage of CO2 in the flue gases.
The gas is then driven over into the pipette C and a similar
operation is carried out. The difference between the
resulting reading and the first reading gives the percentage
of oxygen in the flue gases.
The next operation is to drive the gas into the pipette D, the
gas being given a final wash in E, and then passed into the
pipette C to neutralize any hydrochloric acid fumes which
may have been given off by the cuprous chloride solution,
which, especially if it be old, may give off such fumes, thus
increasing the volume of the gases and making the reading
on the burette less than the true amount.
The process must be carried out in the order named, as the
pyrogallol solution will also absorb carbon dioxide, while the
cuprous chloride solution will also absorb oxygen.
[Pg 161]
As the pressure of the gases in the flue is less than the
atmospheric pressure, they will not of themselves flow
through the pipe connecting the flue to the apparatus. The
gas may be drawn into the pipe in the way already described
for filling the apparatus, but this is a tedious method. For
rapid work a rubber bulb aspirator connected to the air
outlet of the cock G will enable a new supply of gas to be
drawn into the pipe, the apparatus then being filled as
already described. Another form of aspirator draws the gas
from the flue in a constant stream, thus insuring a fresh
supply for each sample.
The analysis made by the Orsat apparatus is volumetric; if
the analysis by weight is required, it can be found from the
volumetric analysis as follows:
Multiply the percentages by volume by either the densities or
the molecular weight of each gas, and divide the products by
the sum of all the products; the quotients will be the
percentages by weight. For most work sufficient accuracy is
secured by using the even values of the molecular weights.
The even values of the molecular weights of the gases
appearing in an analysis by an Orsat are:
Carbon Dioxide 44
Carbon Monoxide 28
Oxygen 32
Nitrogen 28
Table 33 indicates the method of converting a volumetric
flue gas analysis into an analysis by weight.

TABLE 33
CONVERSION OF A FLUE GAS ANALYSIS BY
VOLUME TO ONE BY WEIGHT
Analys
Volume
is by
Molecul times
Volum Analysis by Weight
Gas ar Molecul
e Per Cent
Weight ar
Per
Weight
Cent
536.8
Carbon CO 12+(21 17.7
12.2 536.8 =
Dioxide 2 6)
3022.8
11.2
Carbon
.4
Monoxi CO .4 12+16 11.2 =

de
3022.8
220.8
7.3
Oxygen O 6.9 216 220.8 =

3022.8
2254.0
74.6
Nitrogen N 80.5 214 2254.0 =

3022.8
Total 100.0 3022.8 100.0

Application of Formulae and RulesPocahontas coal is


burned in the furnace, a partial ultimate analysis being:
Per Cent
Carbon 82.1
Hydrogen 4.25
Oxygen 2.6
Sulphur 1.6
Ash 6.0
B. t. u., per pound dry 14500
[Pg 162]
The flue gas analysis shows:
Per Cent
CO2 10.7
O 9.0
CO 0.0
N (by difference) 80.3
Determine: The flue gas analysis by weight (see Table 33),
the amount of air required for perfect combustion, the actual
weight of air per pound of fuel, the weight of flue gas per
pound of coal, the heat lost in the chimney gases if the
temperature of these is 500 degrees Fahrenheit, and the ratio
of the air supplied to that theoretically required.
Solution: The theoretical weight of air required for perfect
combustion, per pound of fuel, from formula (11) will be,
.821 .026 .016
10.88
34.5 .
W= ( +( )+ ) = pounds
6 0425 -
.
3 8 8

If the amount of carbon which is burned and passes away as


flue gas is 80 per cent, which would allow for 2.1 per cent of
unburned carbon in terms of the total weight of dry fuel
burned, the weight of dry gas per pound of carbon burned
will be from formula (16):

11 10.7 + 8 9.0 + 7(0 + 80.3)


23.42

W= = poun

ds
3 (10.7 + 0)

and the weight of flue gas per pound of coal burned will be .
80 23.42 = 18.74 pounds.
The heat lost in the flue gases per pound of coal burned will
be from formula (15) and the value 18.74 just determined.
Loss = .24 18.74 (500 - 60) = 1979 B. t. u.
The percentage of heat lost in the flue gases will be 1979
14500 = 13.6 per cent.
The ratio of air supplied per pound of coal to that
theoretically required will be 18.74 10.88 = 1.72 per cent.
The ratio of air supplied per pound of combustible to that
required will be from formula (14):
.803
= 1.73
.803 - 3.782(.09 - 0)

The ratio based on combustible will be greater than the ratio


based on fuel if there is unconsumed carbon in the ash.
Unreliability of CO2 Readings Taken AloneIt is generally
assumed that high CO2 readings are indicative of good
combustion and hence of high efficiency. This is true only in
the sense that such high readings do indicate the small
amount of excess air that usually accompanies good
combustion, and for this reason high CO2 readings alone are
not considered entirely reliable. Wherever an automatic CO2
recorder is used, it should be checked from time to time and
the analysis carried further with a view to ascertaining
whether there is CO present. As the percentage of CO2 in
these gases increases, there is a tendency toward the
presence of CO, which, of course, cannot be shown by a CO2
recorder, and which is often difficult to detect with an Orsat
apparatus. The greatest care should be taken in preparing
the cuprous chloride solution in making analyses and it must
be known to be fresh and capable of absorbing CO. [Pg 163]
In one instance that came to our attention, in using an Orsat
apparatus where the cuprous chloride solution was believed
to be fresh, no CO was indicated in the flue gases but on
passing the same sample into a Hempel apparatus, a
considerable percentage was found. It is not safe, therefore,
to assume without question from a high CO2 reading that the
combustion is correspondingly good, and the question of
excess air alone should be distinguished from that of good
combustion. The effect of a small quantity of CO, say one
per cent, present in the flue gases will have a negligible
influence on the quantity of excess air, but the presence of
such an amount would mean a loss due to the incomplete
combustion of the carbon in the fuel of possibly 4.5 per cent
of the total heat in the fuel burned. When this is considered,
the importance of a complete flue gas analysis is apparent.
Table 34 gives the densities of various gases together with other data that will be of service
in gas analysis work.

TABLE 34

DENSITY OF GASES AT 32 DEGREES FAHRENHEIT AND ATMOSPHERIC


PRESSURE
ADAPTED FROM SMITHSONIAN TABLES
Volume Relative Density,
Weight of of Hydrogen = 1
Specific
Chemical One Cubic One
Gas Gravity
Symbol Foot Pound
Air=1 Exact Approximate
Pounds Cubic
Feet
Oxygen O 1.053 .08922 11.208 15.87 16
Nitrogen N 0.9673 .07829 12.773 13.92 14
Hydrogen H 0.0696 .005621 177.90 1.00 1
Carbon
CO2 1.5291 .12269 8.151 21.83 22
Dioxide
Carbon
CO 0.9672 .07807 12.809 13.89 14
Monoxide
Methane CH4 0.5576 .04470 22.371 7.95 8
Ethane C2H6 1.075 .08379 11.935 14.91 15
Acetylene C2H2 0.920 .07254 13.785 12.91 13
Sulphur
SO2 2.2639 .17862 5.598 31.96 32
Dioxide

Air 1.0000 .08071 12.390
[Pg 164] [Pl 164]
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FOOTNOTES

[28] See Table 31, page 151.

[29] This formula is equivalent to (10) given in chapter on combustion. 34.56 = theoretical
air required for combustion of one pound of H (see Table 31).

[30] For degree of accuracy of this formula, see Transactions, A. S. M. E., Volume XXI,
1900, page 94.

[31] For loss per pound of coal multiply by per cent of carbon in coal by ultimate analysis.

[32] For loss per pound of coal multiply by per cent of carbon in coal by ultimate analysis.

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