Ammonia Desorption by Diffused Aeration

Author(s): Embar G. Srinath and Raymond C. Loehr

Source: Journal (Water Pollution Control Federation), Vol. 46, No. 8 (Aug., 1974), pp. 1939-1957
Published by: Water Environment Federation
Stable URL: http://www.jstor.org/stable/25038213
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Ammonia desorption by diffused aeration
Embar G. Srinath and Raymond C. Loehr

In water, ammonia exists in equilibrium

Control
is of of nitrogen
increasing in wastewaters
importance. Ordi with ammonium ion,
narily, most of the nitrogen in untreated NH4+ + H20 ** NH3 + H30+ ( 1 )
wastewaters exists as ammonium nitrogen,
permitting nitrogen control by ammonia The quantity of undissociated ammonia
desorption. Ammonia loss can occur (NH3-N) is a function of pH and the
wherever a gas unsaturated with ammonia ionization constants of aqueous ammonia,
moves past the surface of a liquid that kb, and water, kw, that is,
has free ammonia available for desorption. 10pff
Natural ammonia losses can occur in aer NH3-N = (NH4-N) X t- (2)
ated waste treatment systems, open ponds
and reservoirs, and streams. ^ + 10^
Kw
or
Knowledge of how process design and
environmental factors affect ammonia de
undissociated ammonia-nitrogen _
sorption rates and knowledge of the mag
total ammoniacal nitrogen
nitude of the desorption rates are essential
to the use of ammonia desorption as a ni
trogen control process. Information on T^- = F (3)
the rates of ammonia loss during natural
and artificial aeration is also useful for
Kw ^ + 10^
(a) the proper design of treatment pro where F is the ratio of the undissociated
cesses, (b) a better assessment of nitro ammonia to the total ammoniacal nitrogen
gen balances in treatment systems, and (NH4-N) in the solution. The undis
(c) a better understanding of the possible sociated (free) ammonia is the ammonia
nitrogen losses in natural systems. This in solution that can be removed by
paper describes theoretical considerations desorption.
to predict ammonia desorption from wa The variation of F with pH and tem
ters and wastewaters, experiments on re perature, which affects kb and kw, is shown
moval of ammonia from wastewaters by in Figure 1. Because the amount of am
diffused aeration, and predictive equations monia desorbed is directly proportional to
that relate ammonia desorption efficiency the concentration of undissociated am
to environmental and process conditions. monia, higher pH values and temperature
favor desorption.
Theoretical Considerations Data indicate that kb and fc?, increase
with an increase in temperature.1 Math
In a given time, the quantity of am ematically, the relationship between the
monia desorbed from a solution depends value of fc?/fcw and temperature may be
on (a) concentration of undissociated am expressed as
monia, (b) gas-liquid surface area, (c) h/kw= [-3.398 ln(0.0241
mass-transfer coefficient, and (d) partial
pressure exerted by ammonia in the gas
x 0?C)]xlO9 (4)
phase. These, in turn, are influenced by Values of F for specific pH values and
environmental and process conditions. temperatures are noted in the Appendix,

-Vol. 46, No. 8, August 1974 1939

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Srinath and Loehr

pH
FIGURE 1.?-Effect of pH and temperature on fraction of un
dissociated ammonia.

Table A-l, and are based on the values of During the removal of ammonia from an
kb and kw available elsewhere.1 These dis aqueous solution by air stripping, the
sociation constants are based on electro greatest resistance to mass transfer occurs
chemical measurements using very dilute in the transfer from the liquid to the gas
solutions. Recent studies2 have implied phase. This gas phase resistance results
that the value of k^/lcw is influenced by or from the high solubility and ionization of
ganic matter content in a slurry at solids ammonia in water.
concentrations ranging from 3.5 to 8.5 per During ammonia removal, the molecules
cent. of ammonia escape from the liquid phase
The desorption of ammonia from waters and the undissociated ammonia in the
involves the contacting of a liquid and a solution will tend to approach equilibrium
gas phase. With wastewaters, the units with air in contact with the liquid. At
may be spray towers, packed column aera equilibrium, the partial pressure of am
tion towers, or diffused air systems. What monia in air will be equal to the partial
ever the mode of contacting, the two phases pressure of ammonia in solution. At a
are brought together to transfer the am given temperature and atmospheric pres
monia. One phase usually flows counter sure, the relationship between the quantity
current to the other in a manner such of ammonia removed (AC), the con
that both the phases are in contact. Am centrations of undissociated ammonia
monia being transferred from the liquid (C-F), the interfacial area of exposure
to the gas phase must pass through the (Ai), and the time (Ai), may be expressed
interface. It is difficult to measure ac as
curately either the length of the transfer
path or the time of contact. Even though -AC^fc-ArC-F'Ai (5)
an interface exists, its geometry is not well where A: is a coefficient of mass transfer.
defined. It may be assumed that both
phases are separated and that transfer This equation implies that greater quanti
resistance layers are formed on either side ties of ammonia can be desorbed by in
of the boundary. It is in these layers, or creasing the time and interfacial area of
films, that the greatest amount of resistance exposure and the concentration of undis
for mass transfer is encountered.3 sociated ammonia in the liquid. This

1940 Journal WPCF

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 Ammonia Desorption

relationship is valid only when the gas monia takes place within the first few
phase is not saturated with ammonia. millimeters of the ascent of the air bubbles
Increase in area of contact can be through the liquid. Because this process
achieved by spraying in towers, falling film of saturation is almost instantaneous, the
in towers, flow of liquid in thin films measured duration of ammonia desorption
over packings in stripping towers, or in the diffused air system is, in effect, a
diffused aeration. In natural systems such measure of the volume of air needed to
as lakes or ponds, increased surface area achieve the observed removal of ammonia.
is provided by ripples and waves caused Continuous-flow systems. At equilibrium,
by winds. In these systems, wind move a mass balance on a continuous-flow aera
ment also provides unsaturated air adjacent tion unit of volume V having a flow rate Q
to the water surface. and total ammonia concentrations Ct and
When air is bubbled through a liquid C2 in the influent and effluent, respectively,
at a fixed rate, the total interfacial area is will show
the sum of all the surface areas of the air
bubbles. With a given diffuser system (C1-C2)Q = KD'F'C2-V (7)
and a known volume of liquid, increasing V/Q is the average liquid retention time
the rate of aeration will increase the inter
in the unit and the average time of de
facial area of contact. The total interfacial
sorption in a continuous-flow system.
area provided by a unit volume of air can Therefore, the change in concentration
be increased within limits by a proper as a result of desorption may be presented
choice of diffuser and a decrease in the
in terms of the hydraulic retention time,
size of the bubbles.
(tHR), as
Batch systems. The amount of am
monia removed from a liquid in a diffused
aeration system depends on concentration
--p;- = Kd'F'?hr (8)
of ammonium nitrogen, pH, temperature,
rate of air flow, volume of liquid, duration Variable pH. Equations 5 through 8
of desorption, and mass transfer coefficient. are valid for systems where F is constant.
Equation 5 can be used for batch diffused To examine systems in which ammonia
aeration desorption systems. Because of desorption is accompanied by a change in
the difficulty of measuring or estimating pH, modifications of the equations are
Ah k and A* can be combined into an necessary. When a solution of an am
operational desorption coefficient, KD. KD monium salt is made alkaline, ammonium
is system-specific, being dependent on en
ion is converted into undissociated am
vironmental and process conditions. With monia (Equation 1). If ammonia is
desorbed from the alkaline solution and
this modification, Equation 5 may be writ
ten as the pH of the system is not maintained
constant, then the pH will decrease, re
sulting in a decrease in F and in ammonia
ln[?] = KD.F-(t2-h) (6)
loss. The decrease in the pH value is
linear with respect to time (Figure 2), and
where Cj and C2 are the concentrations of the decrease in ammonia concentration is
total ammoniacal nitrogen at times tt and logarithmic with time.4
t2, respectively.
The partial pressure exerted by am In Ct = In C0 - a-i (9)
monia in air is very low. It takes only a pHt = pH0-z't (10)
very small amount of ammonia deserted
from the liquid to saturate the air. No fur where pHt and pH0, and Ct and C0 are the
ther desorption takes place after the gas values of pH and ammonium concentrations
phase has been saturated with ammonia. at times t and 0, respectively, and a and z
In diffused air systems, saturation with am are constants.

-Vol. 46, No. 8, August 1974 1941

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 Srinath and Loehr

Designating ln(10pH + h/ky,) as L and

using appropriate subscripts for L to denote
the values at different pH, Equation 13
^ 400
z can be condensed to
? -pH
z
UJ
? 300
o
oc In(C2/Cl) = ,dn 10) (14)
z
Because z is the slope of the pH-time curve,
3 200
- (PH*-pH?)(]n O/&)Qn 10) ....
Kd~ h-hHU-Lt) (15)
The values of L at different temperatures
and pH are noted in the Appendix, Table
15 30 45 60 A-2.
AERATION TIME ( mi ?ut??)
Use of Henry's law. The air bubbles
emerging from an ammonia desorption
FIGURE 2.?Rate of change of pH and system will be saturated with ammonia,
ammonium concentration during desorp and the concentration of ammonia in the
tion from a system in which pH is not air bubbles will be in equilibrium with
controlled (laboratory experiments). the concentration of ammonia in the
liquid. The quantity of ammonia removed
It would be useful to develop relation from the liquid will equal the ammonia
ships between pH, time, concentration of in the air diffused through the liquid,
total ammonia in the liquid, and KD for
predictive and design purposes. Since F
V-AC = A-Ai-p>a (16)
is a function of pH, Equation 6 may be where
rewritten as follows by using Equation 3:
V ? volume of the liquid,
dC AC = change in NH4+-N concentration
? = -KDF-dt
in the liquid that occurred by
10** desorption in time Ai,
^[t?SFXT?-T^
10** + (kb/kw) M' i") p ? partial pressure of ammonia in air,
pa ? density of ammonia, and
When the rate of aeration and temperature A = air flow rate.
are constant, the values of KD and k^/Jc?,
do not vary. Under these conditions, when According to Henry's law, p is related
pH is allowed to fall as ammonia is de to the ammonia concentration of the liquid,
sorbed, C, pH, and t are the only variables.
C-F
Combining Equations 10 and 11 results P = ~ (17)
in Equation 12,
dC r iopHo-zt -i where C F is the free ammonia concentra
C tion in the liquid, and H is the solubility
-KDL(kb/kw) + io^-*<\'dt (12)
coefficient of NH3. This relationship is sys
If pHi and Ci are conditions at time ty tem- and temperature-dependent. Henry's
and pH2 and C2 are conditions at time law must be used with great care when one
t2, Equation 12 may be integrated to
is dealing with a gas, such as ammonia,
having considerable affinity for a solvent.5
ln(C2/Ci) z= In
Kd10 Henry's law is apparently valid for an air
water-ammonia system if corrections are
[ In(10**? + h/kw) - In(10"*i + kh/kw)~] made for the ionization of ammonia in
(13) water. By using Equation 17, Equation
1942 Journal WPCF

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 Ammonia Desorption

16 may be written as The samples of poultry and dairy manure

used in these experiments were collected
V-C = A-t-?-pa (18) from facilities at Cornell University, Ithaca,
N. Y. The oxidation ditch was located
and in the Agricultural Waste Management
Laboratory at Cornell.

4:-(??) ' e--? (l9) fluence

To correlate the factors that may in
desorption of ammonia from waste
waters, and to characterize the wastewaters,
Comparing Equation 19 with Equation 6,
analyses were made for all forms of nitro
it is apparent that KD is the equivalent of
gen, pH, total solids (ts), chemical oxygen
the factors in parentheses in Equation 19.
Thus, if H is known or can be estimated, demand (cod), and viscosity.
Total solids, total Kjeldahl nitrogen, am
it is possible to use Henry's law to estimate
monia, nitrite, and nitrate nitrogen were
the quantity of air needed for ammonia
desorption. If desorption data are avail determined by the methods described in
"Standard Methods."6 The cod of the
able, 19 can also be used to determine
values of H. samples was determined by the modified
method.7 The pH was measured with a
pH meter.
Evaluation of Kd To measure the viscosity of the liquids,
Knowledge of KD is important to the an Ostwald constant-volume flow capillary
understanding of ammonia desorption sys viscometer was used. To separate particu
tems. With KD known or estimated, de late matter in the wastes that may have
sorption times and pH levels can be clogged the capillary, the suspensions were
identified to obtain required ammonia loss, filtered through tissue paper before the
or the ammonia losses that do occur in analysis. Viscosity of some of the samples
natural or artificial aerated systems can be was also measured by a Brookfield rota
evaluated. All of the previous equations tional viscometer. For measurements with
assume that the rates of ammonia produc this viscometer, separation of the particulate
tion from organic nitrogen and the rates matter was not necessary.
of nitrification are negligible. Where this Experiments. Small- and large-scale
assumption is not valid, the mass balances experiments were made on batch and con
on the system must include these factors. tinuous-flow units with diffused aeration.
KD, however, is independent of these rates Small-scale experiments. Batch and con
of ammonia change. tinuous-flow laboratory units were used.
KD is system-dependent, being a function The air used for desorption was monitored
of both environmental and process condi in a rotameter and was saturated to avoid
tions. To obtain greater information on excessive evaporation. Many runs were
how KD is affected by environmental fac made at room temperature, 20? to 23 ?C.
tors, a series of laboratory and pilot-plant In other runs, the temperature of the
experiments were conducted with various system was kept constant by immersion of
concentrations of ammonia in water and the units in a constant-temperature water
wastewaters. bath. In the continuous-flow units, a con
Materials and experimental methods. stant flow into the desorption units was
Experiments on desorption of ammonia maintained with the aid of an "electrolysis
were conducted with the following liquids: pump." 8 A constant detention volume was
(a) solutions of different concentrations of maintained in each experimental run.
ammonium chloride in water, (b) suspen A battery of continuous-flow units was
sions of poultry manure in tap water, (c) used by connecting a number of cylindrical
suspensions of dairy manure in tap water, vessels of different dimensions in series
and (d) mixed liquor from an oxidation (Figure 3). By adjusting the height of
ditch treating poultry wastes. the outlet on the last vessel, different de

-Vol. 46, No. 8, August 1974 1943

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Srinath and Loehr
AIR FLOW METERS
trolled. Eighteen separate batch runs were
made at constant pH with poultry waste
suspensions and solutions of ammonium
chloride in tap water. Thirty-eight large
scale trials were made. Of these, 20 were
LIQUID LEVEL batch runs.
/ INFLOW Small-scale experiments. Constant pH.
Foaming occurred when suspensions of
poultry wastes were aerated. Dow Corn
TYGON TUBING ing silicone antifoam was used to reduce
foaming. In separate experiments, KD was
FIGURE 3.?Schematic diagram of con found not to be affected by the antifoam
tinuous-flow laboratory apparatus for am at the concentrations used.
monia desorption. The effects of the following parameters
were studied: (a) concentrations of total
tention volumes could be obtained. With ammonia from 50 to 1,000 mg/1 as N, (b)
this arrangement it was possible to examine, values of pH from 9 to 11, and (c) aera
in the same run, the effects of detention tion rates from 0.5 to 2.5 cfm (0.014 to
time, rate of aeration, pH, and concentra 0.07 cu m/min). These rates reflect the
tion of ammonia on the desorption of am uncorrected rates of air flow. Subsequent
monia from the liquid. data reported in the paper are air flows cor
rected to standard conditions. The pH
Pilot-plant experiments. The batch units
setup was similar to that for the small value of the liquid was readjusted periodi
scale experiments. The desorption tank cally to the desired level throughout a run,
was a 7-ft (2.1-m) high cylindrical vessel, about every 10 to 15 min, especially for the
3 ft ( 0.9 m ) in diam. The air was diffused runs in which pH value of the liquids was
through a 3-ft (0.9-m) long perforated high.
pipe. The maximum air flow rate obtain First-order reaction rates were observed
able was 30 scfm (0.84 cu m/min). with the liquids used in these experiments
In the continuous-flow unit the desorp (Figure 4). The desorption coefficient did
tion tank was a cylindrical vessel 3 ft not vary with initial total ammonia nitrogen
(0.9 m) in diam with outlets at different concentrations in tap water.
heights. Different detention volumes could
be obtained by proper choice of outlet. 1000
Constant flows of the liquid and of a
solution of sodium hydroxide were main
tained with the aid of peristaltic pumps.
Waste suspensions for the pilot-plant
experiments were stored in a 900-gal
(3,400-1) tank and gently aerated to keep
solids in suspension. The change in am
monia concentration was negligible in this
tank.
Results
The small-scale experiments consisted
of 25, 51, 17, and 27 separate runs made, 20 40 60 80
respectively, with solutions of amonium AERATION TIME-minutas
chloride in tap water, suspensions of
poultry manure, poultry waste treated by FIGURE 4.?Desorption of ammonia in
oxidation ditch, and suspensions of dairy batch units at controlled pH. (Cfm X
manure. In these runs, pH was not con 0.028 = cu m/min.)

1944 Journal WPCF

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 Ammonia Desorption

Uncontrolled pH. No attempts were

made to adjust the pH value in these ex
periments. The experimental procedure
in these runs consisted of analyzing sam
ples taken from the aeration units at specific
intervals for temperature, total ammonia,
pH, and ts.
During aeration, the temperature of the
liquid and the value of KD decreased.
With higher rates of air flow, greater re
ductions in the liquid temperatures oc .4 .6 .8 1.0
curred. To determine the effect of tem
KD PER HOUR
perature on the rate of desorption of am
monia by aeration, a specific series of 6 SCFH/L I2SCFH/L
experiments was conducted. The liquids
were maintained at a constant temperature SCFH/L
by a water bath. The experiments were
conducted at 10?, 15?, 20?, 25?, 30?, and
35 ?C, and the values of KD were deter
mined at air flow rates of 6, 10, 12, and 20
scfh/1 (0.17, 0.28,0.33, and 0.56 cum/hr/1).
The results of these experiments (Fig
ure 5) indicated that with an increase in
either temperature or rate of air flow
through the system, KD increased. The
intercepts of the air flow-K^ lines had a K0 PER HOUR
positive intercept on the x axis, indicating
that ammonia desorption can occur even FIGURE 5.?Effect of temperature and
when there is no aeration. The value of air flow on ammonia desorption rate con
this intercept is an estimate of the rate of stant. ( Cu ft X 0.028 =cu m. )
ammonia loss that could occur under
quiescent conditions in bodies or containers ship may be expressed as
of water and wastewater.
The intercepts of the temperature-Ki)
KD = a(^ (20)
lines (Figure 5) have a positive intercept where
on the y axis, indicating that the desorp [x = viscosity of the liquid,
tion of ammonia can occur only at tem b = slope of the lines in Figure 6, and
peratures greater than about 3?C. The a = value of KD when ?i is 1 centipoise.
slope of these lines provides an estimate
of the effect of temperature on the effi A comparison of the slopes, b, indicated
ciency of ammonia desorption and the that neither the type of liquid nor the air
ability to predict the effect of changes in flow rate within the range of 6 to 20 scfh/1
ambient conditions on the process. (0.17 to 0.56 cu m/hr/1) of liquid had a
A comparison of the viscosity at differ significant effect. A slight difference in
ent temperatures and the corresponding this relationship was noted at an air flow
values of KD at a given rate of aeration rate of 3 scfh/1 (0.09 cu m/hr/1). The
indicated a linear relationship on a log value of a represents an estimate of the
log plot (Figure 6). The data presented maximum KD value that can be obtained
in Figure 6 were obtained over a tem at the noted air flow rates.
perature range of 10? to 30?C. With an Suspensions containing various amounts
increase in the viscosity there was a pro of the wastes were used to evaluate the
portionate decrease in KD. This relation effect of viscosity and ts content on KD.

-Vol. 46, No. 8, August 1974 1945

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 Srinath and Loehr
1.0
hydroxide were used to adjust the initial
.8 ^POULTRY 3-3 SCFH/L pH of the liquids, which ranged from 8.5
WASTE -6 SClrH/L to 12.0. In these studies, pH was not con
o-IO SCFH/L trolled, and pH values decreased naturally
-12 SCFH/L in the runs as the ammonia was desorbed.
WASTE -20 SCFH/L Batch units. When fresh waste was
tr used, the ammonia content of the suspen
O .4 sion increased because of the conversion
X
of organic nitrogen to ammonia nitrogen,
O and it was difficult to determine the value
OXIDATION of KD for suspensions of fresh manures.
OITCH LIQUID Consequently, the wastes were "aged" be
fore use by keeping them moist for 10
.2 POULTRY
days to insure biological conversion of or
ganic nitrogen to ammonia. Lime and
sodium hydroxide were used to control pH.
DAIRY When the quantity of the poultry manure
exceeded 50 lb/150 gal (23 kg/570 1), the
viscosity of the suspensions increased after
I246 about 24 hr of aeration coincidental with
VISCOSITY- ctntipoists a decrease in the value of KD. The change
in viscosity occurred with both bases and
FIGURE 6.?Effect of viscosity on rate of was caused by the solubilization of organic
ammonia desorption. (Cu ft X 0.028 = matter.
eu m.) The results of this study confirmed pre
vious relationships indicated in Equation
The viscosity of the suspensions increased 20. The slopes of these lines, the b value
with increase in the solids content. With in Equation 20, ranged from ?3.4 to ?3.7
all other conditions remaining constant, with an average of ?3.5 in both these
higher air flow rates are required to ac large-scale experiments and the bench
complish a given degree of ammonia re scale experiments. These values may dif
moval with an increase in the viscosity of fer if problems of representative sampling
a liquid. are encountered.
Large-scale experiments. Large-scale When the supernatant liquid containing
experiments were conducted to verify re all the ammonia nitrogen was decanted
sults of the small-scale studies and to and used for desorption, the problem of
examine the practical problems that may thickening of the liquid was overcome and
be encountered with large-scale installa the value of KD remained the same even
tions. In these batch studies, ammonium after 5 days of aeration. The viscosity
chloride and poultry waste suspensions of the liquid did not change during these
were used, while in these continuous-flow runs.
systems, only the poultry wastes were used.Continuous-flow units. The results of
The volumes of liquid used ranged from these continuous-flow experiments verified
150 to 450 gal (570 to 1,700 1) so that that Equation 8 could be used to predict
various air flow rates to liquid volumes values of KD using actual data, and can
could be evaluated. The experiments were be used for large-scale continuous am
conducted at laboratory temperatures, 18? monia desorption systems. These results
to 22?C. In the continuous-flow studies, also confirmed that the data obtained in
the rates of air flow varied from 4.0 to both laboratory batch and continuous-flow
12 scfh/gal (0.003 to 0.09 cu m/hr/1) units are comparable with those obtained
with detention times varying from 25 to in the larger-scale studies (Figure 7). The
120 hr. Sodium hydroxide and calcium confirmation indicates that data obtained

1946 Journal WPCF

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 Ammonia Desorption
w
from small-scale units can be used to esti z
o
mate the KD values in large-scale batch
and continuous-flow systems. ?S -04
Quality of effluent. The treatment of /
wastes to desorb ammonia also altered the /
/
concentration of other waste characteris o
i /
< .03
tics. The addition of a base to waste
solutions precipitated colloidal material,
reducing a portion of the organic and in
organic content. In some runs, as much S 02 *y
/'
id <
as 80, 58, 77, and 80 percent, respectively, a. in
o tu
of cod, total nitrogen, ammonia, and ortho * <3
phosphates were removed.
/
/
Discussion
Basic data on mass transfer properties
fe.
of liquids are necessary for either design OBSERVED VALUE IN PILOT PLANT TRIALS
ing equipment suitable for desorption of
ammonia from wastewaters or for assess
FIGURE 7.?Comparison of laboratory
ing the performance of systems in which and pilot plant ammonia desorption data.
ammonia losses occur. Some information
is available in chemical engineering litera
ture on absorption of ammonia in liquids. The kinetics of the mass-transfer process
Little work, if any, has been done on am for desorption of ammonia from water or
monia desorption, and data on rates of wastewater are complicated by ionic equi
interchange of gases other than oxygen libria. In the reaction of ammonia with
during aeration are meager. In general, water to form ammonium hydroxide, the
it is necessary to determine desorption co quantity of ammonia present in the undis
efficients by direct experiment or to rely sociated form depends on the pH value
on semi-empirical relationships. of the solution and the dissociation constant
The rate of desorption of ammonia from for ammonium ion.
solutions is a function of the variables pre To assess the costs of an ammonia de
viously noted. These studies on desorption sorption unit, it is necessary to know the
of ammonia from water and wastewaters quantities of alkali needed to keep a re
by air stripping have provided useful in quired amount of undissociated ammonia
formation on the important factors that in the system and the duration of treatment
govern the rate of removal of ammonia by needed to achieve a required level of re
aeration. With these data it is possible moval of ammonia. Both of these factors
to predict the extent of removal of am depend on the value of F. Both pH and
monia at different rates of air flow, tem temperature affect the value of F. To
perature, and pH. change the pH of a solution from any
Solubility and pH. The resistance to given point on the pH scale by two units,
mass transfer of ammonia from a liquid it requires 10 times more alkali to accom
to a gaseous phase results from the re plish the second unitary rise. For exam
sistance of the liquid and gas films at the ple, at 20?C, about 60, 94, and 99 percent
interface. Because ammonia is highly of ammonia is in the undissociated form,
soluble in water, its gas film resistance is at pH values of 9.6, 10.6, and 11.6, respec
very high compared with the liquid film tively. The quantity of alkali required
resistance. A large volume of air must for increasing the free ammonia content
be passed through the liquid to remove of a solution of an ammonium salt, in pure
substantial amounts of ammonia. water, from 60 to 94 percent is only one

-Vol. 46, No. 8, August 1974 1947

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Srinath and Loehr

tenth of that needed to increase it from 10,000 mg/1). The value of M for the
94 to 99 percent. The quantity of alkali oxidation ditch mixed liquor, which had
needed to obtain a known level of free a high solids concentration (19,000 to
ammonia will decrease with increase in 28,000 mg/1), was different from the val
temperature. The duration of aeration ues obtained for the other liquids. For
needed to accomplish a required degree specific air:liquid ratios, the M value and,
of ammonia removal is inversely related therefore, the KD value appeared to de
to the value of F. pend on the solids content of the liquids.
The optimal value of pH in the treat The high solids content affected the rheo
ment process depends on the economic logical properties of the liquids.
factors, balancing the costs of alkali and By using the M values determined in
tank size against the savings in time and these studies, it may be possible to predict
costs of aeration and pumping. These and KD for any waste having a solids content
other studies indicate that the pH value similar to those of the liquids that were
of an ammonia desorption system will used. The values of M may be system
have to be raised to about 10.5 to main dependent.
tain the level of undissociated ammonia at When the values of M were plotted
about 95 percent. against temperature, a straight line was
Effect of rate of aeration at different obtained (Figure 8), which may be ex
temperatures. At any temperature, higher pressed as
values of KD can be obtained by increasing
the rate of aeration. The relationship of
Me-m? + ? (22)
KD to air flow rate, A, per liter of liquid, where Me is the slope of the air flow per
LQ, was linear (Figure 5) and may be liquid volume to KD relationship at a tem
expressed as perature 6, and m and ? are constants.
Values of these constants for the authors'
?- = MKD + D0 (21) experiments are given in Table I.
Equation 18 permits the determination
where D0 is the intercept on the x axis of M and, hence, KD at any temperature
and expands the usefulness of previous
and is numerically equal to the rate of
desorption of ammonia when there is no relationships to permit the evaluation of
the effect of different air flow rates and
aeration. The value of D0 is small com
pared with MKD when diffused aeration is liquid volumes over a wide temperature
range. The differences in m noted in Fig
used for desorption. For these practical
situations, D0 may be considered to be ure 8 were not thought significant. It is
zero. likely that the average value can be used
If desired, the value of M can be de for water, poultry manure wastewater, and
dairy manure wastewater.
termined from specific laboratory or largerIndividual values of KD were increased
scale experiments with known A:LQ ra
tios and KD values. The value of M de by a factor of 1.5 to 2 when the tempera
pends on temperature and decreases with ture was raised by 10? C. This suggests
increasing temperature. Knowledge of that the following empirical relationship
the value of M can be useful in calculat may be used for temperature and KD in
the temperature range of 10? to 35?C:
ing the value of KD at different air flow
rates or different ratios of air rates to
KD2 = KDlE?*-** (23)
liquid volume. The M values for water,
poultry manure wastewater, and dairy where KDl and KD2 are the desorption
manure wastewater were similar at com rates at the same rate of air flow at tem
mon temperatures, that is, 72 to 77 at 15?Cperatures 0i and 02. The values of E were
and 63 to 69 at 20?C. All of these liquids in the range of 1.06 to 1.065, with a mean
had low solids concentrations (4,000 to of 1.063.

1948 Journal WPCF

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 Ammonia Desorption

1201

3 ,0?J
m-SCF/LITER/?C
2i 80
7POULTRY
WASTE
< 60 DAIRY ^
WASTE

40 WATER ^ ^>
N^s
C*S
v^S
2a
10 20 30 40
TEMPERATURE - ?C

FIGURE 8.?Effect of temperature on slope of K?:air flow

ratio. ( Cu ft X 0.028 = cum.)

On the basis of the data in Figure 5, may be used for predictive purposes. The
it was possible to develop an empirical equation represents data obtained from
relationship to relate KD, air flow rate, the laboratory and pilot-plant batch and
and temperature. The data suggest that continuous-flow experiments with the in
it is not possible to desorb ammonia at dicated wastes. Insufficient data were
temperatures below about 5?C. This is available to extrapolate use to other waste
in accord with observations by others, who waters.
have reported the practical inability of op When air flow is zero, the losses of am
erating the ammonia stripping process at monia from the systems at different tem
ambient temperatures near 32?F (0?C). peratures would represent D0 values
On the basis of the data collected on air (Equation 21) at the respective tempera
flow rates from 6 to 12 scfh/1 (0.17 to 0.56 tures and may be represented by the fol
cu m/hr/1), the following empirical equa lowing equation:
tion was used to relate Kb, air-flow rate,
KD = 0.021et?-062^-5^ (25)
liquid volume, and temperature in the
range of 5? to 35? C: The results obtained by this equation
are illustrated in Figure 10. The values
KD = 0.021
TABLE I.?Values of m and (3 for the
exp 0.091 ? + 0.062(0 - 5) (24) Equation Me = m? + (5*

The units of the parameters in this equa Liquid \ m \ ?

tion are: A, scfh; LQ> 1; 0, ?C; and KD, Water plus ammonium chloride ?3.04 123.1
per hr. Figure 9 compares the results Poultry manure wastewater ?2.86 [ 121.8
obtained with this equation with the re Dairy manure wastewater ?2.65 114.0
sults obtained from actual experiments.
The comparison indicates that Equation 24 * 0 is in terms of ?C.

--Vol. 46, No. 8, August 1974 1949

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Srinath and Loehr
I.Ot
/
/

0.8
/
/
/
UJ /
5 0.6
UJ
/
/
x
UJ
/
0.44 /
^o
/ oKD=0.02.eC009,^+0062(e-5)3
0.2
KD" H-L

o^#
k^45? 0.2 0.4 0.6 0.8 1.0
KD/HR -CALCULATED
FIGURE 9.?Comparison of experimental ammonia desorption
data with results calculated by equations developed in study.

of D0 obtained from extrapolating the KD air. Results of these "quiescent" experi

air flow data for diffused aeration condi ments have indicated a D0 value of 0.0003/
tions are close to the values obtained from sq cm/hr at 25?C. This value corresponds
quiescent beaker experiments conducted to a diffusivity value of 7.5 X 10"4/sq ft/
in our laboratory to estimate ammonia sec (0.7 sq m/sec), which is about three
losses without aeration. times the value reported for ammonia in
The quantity of ammonia desorbed un chemical engineering literature.
der quiescent conditions depends on sev Recently, observations were made on
eral factors, including atmospheric pressure ammonia desorption from holding ponds.9
and the concentration of ammonia in the These results showed that the rate of am

0 10 15 20 25 30 35
TEMPERATURE- ?C
FIGURE 10.?Ammonia desorption rates under quiescent
conditions.

1950 Journal WPCF

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 Ammonia Desorption

monia release depended mainly on the 5X10

wind velocity. Based on these data, the
calculated rates of ammonia desorption
from holding ponds will be, respectively,
9.3 X 10-8, 9.9 X 10-8, and 1.41 X 10"7/sq
cm/hr at 13?, 14?, and 15? C when the
wind velocity is zero. EXPERIMENTAL
The wide variations in the rate of am
mo*
monia desorption among these studies
could perhaps be explained on the basis
of differences in the conditions under which
ammonia releases occurred. 5X10" THEORETICAL^ \\
(EQ.26) \N
The results given in Figures 9 and 10
verify the validity of Equation 25 when
it is used as a tool for making rough es
timates of the rate of loss of ammonia
from alkaline impoundments, stabilization
ponds, and other large bodies of polluted
water.
IXIO 10 20 30 40
Use of Henry's law. Kowalke et al,15 TEMPERATURE (C?)
on the basis of thermodynamic considera
tions, showed that the partial pressure FIGURE 11.?Values of Henry's constant
exerted by ammonia in the gaseous phase (solubility coefficient) at different tem
depends on the molal concentration of am peratures.
monia in the solution and temperature.
4 425
The values of H calculated by using the
\n(p/m) = 10.82 - ^+"0 (26) data from the authors' experimental studies
where and Equation 19 and the values reported
by other investigators are compared in Fig
p = equilibrium partial pressure of am ure 11. These values of H are in reason
monia in the gaseous phase,
m = molal concentration of ammonia in able agreement with the theoretical values
solution, and of H given by Equation 28.
6 = temperature, ?C.
Earlier statements suggested that KD
could be determined if values of H are
If one uses Equation 17, the partial available (Equation 19). The values of
pressure exerted by ammonia in the gas KD calculated by using Equations 19 and
eous phase by a molar solution of ammonia 28 are included in Figure 9. These values
at different temperatures may be expressed are in close agreement with those obtained
experimentally and by using Equation 24.
Thus, it appears possible to estimate
KD and, therefore, process design factors
for ammonia desorption, by using H and
4,425 Equation 19. Experimental and pilot-scale
= 10-82 - 273 + * (27) data would be useful to verify the results
of such a mathematical estimate.
where H is the solubility coefficient for am
Air requirements. The quantity of air
monia. The value of H is inversely pro
portional to the temperature. Equation required to accomplish a specific ammonia
removal is of interest when desorption of
27 can be simplified as ammonia is considered. The results of these
ff(mg/l - atm)= 3.564 X 106 studies were compared with those of other
X e[-0.0525 x *?C] (28) studies (Table II). Investigators,11-14?18

-Vol. 46, No. 8, August 1974 1951

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CD
Ox
to

o i TABLE II.?Relative Efficiencies of Ammonia Desorption

Process E
Tem Quantity of Initial NH4-N Quantity of
Type of Liquid pH perature Air Used Concentration NH4 Removed Ammonia
(?C) (cu ft/gal) (mg/1) (mg N/gal) Removed
(%)

Other investigations :
Wastewater from 10.5 300 100 321 85
petroleum industry18 9.4 300 100 129 34
8.9 480 100 344 91
8.8 480 100 220 58
Secondary wastewater 8.6-9.3 380-3,040 26 79 80
treatment effluent12 10.1-10.8 750 26 96 98
treatment effluent13 10.5 23 535 31 74 63
treatment effluent14 11.0 23 430 30 100 88
Anaerobic digester
supernatant11 11.2 437 850 2,638 82
This study, diffused aeration :
Poultry waste 10.6 10.4 20 77.5 703 665 25
Dairy waste 10.6 10.4 20 77.5 321 255 21
Oxidation ditch mixed
liquor 10.5-10.0 20 233 150 187 33
Water 10.3-10 20 77.5 560 488 23

Note: Cu ft X 0.028 = eu m.

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 Ammonia Desorption

using an aeration tower for ammonia cause the appropriate KD values are avail
stripping, noted that the quantities of air able from this research.
required for achieving about 90 percent Application to practice. In practice,
removal ranged from 300 to 750 eu ft of the amount of ammonia that must be re
air/gal (2.2 to 5.5 eu m/1) of liquid. The moved is established by environmental
ammonia nitrogen content of their wastes quality considerations such as effluent or
generally was below 30 mg/1. Only in stream quality criteria or the amount that
two of the studies was a waste used having can be included in land disposal of wastes
a higher ammonium content (about 100 without being excessive. With the needed
and 800 mg/1). removal known, the engineer has a num
In the studies reported in this paper, ber of decision variables to consider in
higher quantities of ammonia removed the design of an ammonia desorption sys
per unit of waste or air were observed. tem. These variables include air flow,
More efficient use of the air should occur pH, temperature, and time of desorption.
with concentrated wastes. Where high For a specific waste, the flow and physi
ammonia removals are not required, lower cal characteristics such as viscosity, sur
percentage removals and better air use face tension, and solids content should vary
may be feasible. only within a reasonable range and, in
The amount of ammonia removed per addition, usually cannot be controlled or
unit of air flow, dq/dv, per initial am altered by the design engineer. The en
monia concentration can be related to the gineer has the challenge of determining
initial total ammonia concentration, C, and the best set of design variables to meet
the fraction of undissociated ammonia, F. the needed removal at minimum cost.
The steps that would be taken in arriv
1 da
c? = K?F (29)
ing at the best design are:

1. Determine KD by using the various

To compare all the studies on a common equations in this paper or using samples
basis, unit efficiencies were expressed as of the waste. Determine KD under pos
KVF, and to compare the studies indepen sible air flow and liquid volume relation
dently of F, values of Kv were calculated ships by using diffused aeration laboratory
(Table II). experiments.
The KVF values vary in each study and 2. Investigate other possible values of
among the studies. Generally, the KvF KD over the temperature range likely to
values ranged between 0.001 and 0.012. be found in practice (Equation 23), espe
The Kv values exhibit a similar wide vari cially to determine the effectiveness of re
ation, ranging from 0.001 to 0.03. The moval at low temperatures and to estimate
KVF and Kv values obtained in the authors' the potential of increasing the tempera
studies are within the range of values ture of the waste before desorption.
found in other studies but tend to be on 3. Use either Equation 21 or 24 to in
the higher side, indicating the greater re vestigate other possibilities to vary air flow
moval possible with wastes of high am and liquid volume to obtain optimum de
monia concentration. sorption rates.
pH changes. Equation 15 provides the 4. With possible KD values known, in
opportunity to predict the pH changes vestigate the pH and time relationships
that will occur in a system as the ammonia that will obtain the desired ammonia re
is lost. This prediction can be made for moval in batch systems or the appropriate
both aerated and quiescent systems be pH relationships for continuous systems.

-Vol. 46, No. 8, August 1974 1953

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Srinath and Loehr

If the maximum possible ammonia re An example of the types of alternatives

moval is desired, both KD and F should that could be involved in the removal of
be as large as possible, that is, air flow ammonia from wastewaters may be con
rates, temperature, and pH should be maxi structed by using data obtained in this
mized. However, if less than maximum study. Figure 12 was prepared to illus
removals are adequate, then there are a trate the patterns that could result from
number of possible design tradeoffs be different combinations of air flow rate per
tween KD, F, and time to obtain these re unit of liquid, pH, temperature, and per
movals. The decisions would be made on centage removal. Thus, there are many de
the basis of the relative costs of aeration cisions that may be made to obtain a spe
equipment, base to adjust the pH, tank cific ammonia removal, each requiring
age to obtain the necessary time, and heat different desorption times to accomplish
to adjust the temperature. Maximum pH the desired results.
levels, aeration rates, time, or temperature As observed from Figure 12, little dif
may not be necessary if intermediate am ference in desorption time occurs at pH
monia removals are adequate. values of 10 to 11 at temperatures from
5. Scale up the best data obtained above 10? to 25?C. Below a pH of 10, the time
for a system to meet the required ammonia needed to accomplish a specific removal
removal needs. increased rapidly. Higher removal effi
6. Determine the capital and operating ciencies required increased desorption
costs of the various alternatives, and de times. The time needed to accomplish
termine the optimum combinations of vari 75-percent removal was double that needed
ables to produce the least expensive to accomplish 50-percent romoval at 20 ?C.
systems. Similarly, it would take twice as much

4001

20?C
15 SCFH
o
50% REMOVAL UJ
60-1 10 SCFH
300 4
z2
it REMOVALS
a. co
O Q? 200 J
O
?<
?2
PS
to 2
O
?? 100
X

9 10 II
TEMPERATURE-?C PH
FIGURE 12.?Desorption time needed to obtain specific ammonia removals as a func
tion of temperature and pH. (Cu ft X 0.028 = cum.)

1954 Journal WPCF

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 Ammonia Desorption

time to accomplish 99-percent removal as plicit in the relationships that have been
to accomplish 90-percent. presented is the assumption that the change
A change in temperature affected the de in ammonia concentration of a wastewater
sorption time. At a pH of 10 to 11, a is caused only by ammonia desorption. A
10 ?C temperature drop doubled the time direct application of these relationships to
necessary to obtain a specific removal; at predict ammonia concentrations in the
a pH of 8 to 9, a 5?C temperature decrease effluents would not be possible in treat
doubled the desorption time necessary to ment systems in which the organic nitrogen
achieve the desired removal. The greater is undergoing rapid transformations, re
temperature effect at the lower pH values sulting in a steady increase in ammonia
occurs because of the cumulative effect of concentration of the liquid, while ammonia
pH on the free ammonia concentration and desorption is also occurring simultaneously.
the effect of temperature on KD. It also would not be possible in systems
Decreasing the air flow rate by 5 scfh/1 where simultaneous ammonia desorption
(0.14 cu m/hr/1) increased the desorption and ammonia oxidation are occurring. In
time by a factor of about 1.6, while de such cases, modifications of the relation
creasing the air flow rate by 10 scfh/1 ships should be explored.
(0.28 cu m/hr/1) increased the time by a Nitrogen balances can now be better
factor of about 2.5. The changes noted in evaluated because the equations in this
Figure 12 follow the theoretical relation paper permit better estimates of the am
ship governing the desorption of ammonia monia lost from artificial and natural aer
from diffused aeration systems. ated systems. With the amount of am
Ammonia desorption may reduce the monia volatilized known, one can better
amount of nitrogen in wastes spread or estimate its effect on the local environ
disposed of on the land, thereby decreas ment.
ing any possibilities of excess nitrogen and Detailed equations have been developed
environmental quality problems. In addi to determine the ammonia desorption co
tion, the knowledge obtained in this study efficient, KD, under quiescent and aerated
concerning ammonia desorption may be conditions. Other equations were devel
useful in many other studies. oped to determine the quantity of am
monia lost under a variety of environmental
Summary conditions. All equations were verified in
both laboratory and pilot-plant scale ex
The mathematical relationships de periments. The KD values determined in
scribed in this paper are useful for deter these studies ranged from 0.004 to 0.8/hr,
mining the rates of ammonia desorption depending on process conditions.
under a variety of conditions. Such in
formation is useful in assessing perform Acknowledgments
ance of systems in which ammonia is re
moved either intentionally or unintention Credits. The research reported in this
ally. In many natural systems, ammonia paper was obtained as part of the follow
is lost as a result of other processes. Ex ing projects sponsored by the Environ
amples would be losses from aerated bio mental Protection Agency: 13040 DPA
logical treatment systems, swift streams, "Tertiary Treatment of Animal Wastewa
impoundments, aerated odor control sys ters" and 13040 DDG "Animal Waste Man
tems, and waste storage units. agement?Demonstration of Feasible Han
The rate of diffusion of ammonia from dling and Treatment Methods. " The
its aqueous solution into a steady flow of assistance of T. B. S. Prakasam in review
air is influenced by pH, temperature, and ing the research results and the final
viscosity, as well as other variables. Im project report was gratefully appreciated.

-Vol. 46, No. 8, August 1974 1955

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Srinath and Loehr

Greater detail on this topic and other re
sults can be found in the final project
report.4
Authors. E. G. Srinath and Raymond 10. Melamed, A., and Saliternik, C, "Removal
C. Loehr are, respectively, research asso
ciate, Agricultural Waste Management
Program, and professor of Civil and Agri
cultural Engineering, Cornell University,
Ithaca, N. Y.
References 11. Bennet, G. E., "Development of a Pilot Plant
1. "Handbook of Physics and Chemistry/' 47th
Ed., Chemical Rubber Company, Ohio
(1966-67).
2. Hashimoto, A. G., and Ludington, D. C,
"Ammonia Desorption from Concentrated
Chicken Manure Slurries. " Proc. Intl
Symp. Livestock Wastes, Amer. Soc. Agr.
Engr., p. 117 (1971).
3. Lewis, W. K., and Whitman, W. G., "Prin
ciples of Gas Absorption/' Ind. & Eng.
Chem., 16, 1215 (1924).
4. Loehr, R. C, et al, "Development and Dem
onstration of Nutrient Removal from Ani
mal Wastes." Environmental Protection 15. Kowalke, O. L., et al, "Transfer Coefficients
Technology Ser., EPA-R2-73-095 (1973).
5. Hougen, O. A., and Watson, K. M., "Indus
trial Chemical Calculations." 2nd Ed.,
John Wiley & Sons, Inc., New York, N. Y.
(1947).
6. "Standard Methods for the Examination of
Water and Wastewater." 12th Ed., Amer.
Pub. Health Assn., New York, N. Y. (1965). 17. Benneworth, N. E., and Morris, N. G., "Re
7. Jeris, J. S., "A Rapid COD Test." Water
?- Wastes Eng., 4, 89 (1967).
8. Symons, J. M., "Simple, Continuous Flow,
Low and Variable Rate Pumps/' Jour.
Water Poll Control Fed., 35, 1480 (1963).
9. Folkman, Y., and Wachs, A. M., "Nitrogen
Removal Through Ammonia Release from
Holding Ponds." Paper presented at 6th
International Water Pollution Research
Conf., Jerusalem, Israel (1972).
of Nitrogen by Ammonia Emissions from
Water Surfaces." In "Developments in
Water Quality Research: Proceedings of
the Jerusalem International Conference on
Water Quality and Pollution Research."
H. I. Shuval [Ed.], Ann Arbor-Humphrey
Science Publishers, Ann Arbor-London,
165 (1970).
to Demonstrate Removal of Carbonaceous,
Nitrogenous, and Phosphorus Materials from
Anaerobic Supernatant and Related Process
Streams." Rept. of Project 17010 FKA,
FWQA, Dept. of Int. (1970).
12. Culp, G., and Slechta, A., "Nitrogen Removal
from Waste Effluents." Pub. Works, 97,
90 (1966).
13. Kuhn, P. A., "Removal of Ammonium Nitro
gen from Sewage Effluent." M.S. thesis,
Univ. of Wisconsin, Madison (1956).
14. Nesselson, E. J., "Removal of Inorganic Ni
trogen from Sewage Effluent." Ph.D.
thesis, Univ. of Wisconsin, Madison (1953).
of Ammonia in Absorption Towers." Bull
Univ. Wis. Eng. Expt. Sta., Ser. No. 68,
1 (1925).
16. Bayley, R. W., "Desorption of Waste-Water
Gases in Air." Effl. 6- Water TH. Jour.
(London), 7 (Parts 1 & 2), 78 and 115
(1967).
moval of Ammonia by Air Stripping."
Water Poll Control (G. B.), 71 (Part 5),
485 (1972).
18. Prather, B. V., "Wastewater Aeration May Be
Key to More Efficient Removal of Impuri
ties." Oil and Gas Jour., 57, 49, 78 ( 1959).

APPENDIX

TABLE A-l.?Values of F at Different pH and Temperatures4

pH
Temperature
(?C)
7.0 7.5 8.0 8.5 9.0 9.5 10.0 10.5 11.0

10 0.002 0.006 0.020 0.061 0.170 0.393 0.672 0.866 0.953

15 0.003 0.009 0.028 0.082 0.221 0.473 0.739 0.900 0.966
20 0.004 0.012 0.037 0.110 0.280 0.552 0.796 0.925 0.975
25 0.005 0.017 0.052 0.148 0.354 0.634 0.846 0.945 0.982
30 0.008 0.025 0.076 0.207 0.452 0.723 0.892 0.963 0.988
35 0.014 0.043 0.125 0.312 0.589 0.819 0.935 0.978 0.993

1956 Journal WPCF

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 Ammonia Desorption

TABLE A-2.? Values of L at Different Temperatures and pH Values4

Temperature (?C)
pH
10 15 18 20 22 24 26 30 32 35

8.0 22.3295 22.0122 21.8287 21.7048 21.5777 21.4455 21.3066 20.9962 20.8169 20.4986
8.2 22.3412 22.0282 21.8479 21.7265 21.6023 21.4735 21.3387 21.0397 20.8688 20.5692
8.4 22.3594 22.0530 21.8776 21.7599 21.6400 21.5163 21.3876 21.1051 20.9459 20.6719
8.6 22.3876 22.0912 21.9228 21.8107 21.6971 21.5807 21.4605 21.2007 21.0571 20.8157
8.8 22.4307 22.1488 21.9907 21.8862 21.7814 21.6749 21.5661 21.3356 21.2113 21.0082
9.0 22.4955 22.1873 22.0895 21.9954 21.9019 21.8081 21.7136 21.5180 21.4155 21.2532
9.2 22.5903 22.3552 22.2286 22.1472 22.0674 21.9885 21.9102 21.7524 21.6722 21.5490
9.4 22.7242 22.5218 22.4157 22.3487 22.2839 22.2209 22.1593 22.0385 21.9789 21.8897
9.6 22.9054 22.7395 22.6550 22.6027 22.5528 22.5050 22.4590 22.3709 22.3285 22.2665
9.8 23.1386 23.0096 22.9457 22.9069 22.8703 22.8357 22.8029 22.7413 22.7122 22.6704
10.0 23.4236 23.3281 23.2821 23.2545 23.2288 23.2047 23.1822 23.1404 23.1210 23.0934
10.2 23.7550 23.6874 23.6555 23.6366 23.6191 23.6029 23.5878 23.5602 23.5474 23.5295
10.4 24.1246 24.0783 24.0569 24.0442 24.0327 24.0220 24.0121 23.9941 23.9859 23.9743
10.6 24.5231 24.4923 24.4782 24.4699 24.4624 24.4554 24.4490 24.4374 24.4322 24.4248
10.8 24.9425 24.9223 24.9132 24.9078 24.9030 24.8985 24.8944 24.8870 24.8836 24.8789
11.0 25.3761 25.3631 25.3572 25.3538 25.3507 25.3478 25.3452 25.3405 25.3384 25.3354
11.2 25.8193 25.8110 25.8072 25.8050 25.8030 25.8012 25.7996 25.7966 25.7952 25.7934
11.4 26.2687 26.2634 26.2610 26.2596 26.2584 26.2572 26.2562 26.2543 26.2534 26.2522

-Vol. 46, No. 8, August 1974 1957

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