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1512

COMBINATION OF

C02

WITH

OH-

THE KINETICS OF COMBINATION OF CARBON DIOXIDE

WITH HYDROXIDE IONS
BY B. R. W. PINSENT,L. PEARSON
AND F. J. W. ROUGHTON
Dept. of Colloid Science, University of Cambridge
Received 24th April, 1956

The velocity constant k", of the reaction C02 OH- + HC03- has been determined
by the rapid thermal method over the range 0 to 40" C, by mixing together CO;! solutions
with NaOH solutions of concentrations, 0.005 to 0.05 M. The effect of large variations
of ionic strength has also been studied. The present thermal results are considerably
more extensive than any hitherto available, but check satisfactorily with the more limited
data obtained by Faurholt's carbamino method and by the manometric method.
The velocity constant is related to temperature by the equation log k" = 13.635 (2895/T). The energy of activation is 13,250 cal.
Previous manometric figures for the velocity constant k, of the reaction CO2 + H20 -+
H2CO3 have been corrected with the aid of the present values of k". The corrections were
very slight at 0" C but quite appreciable at 25-38' C.
In an earlier paper two of us (Pinsent and Roughton) reported values of k,,
the velocity constant of the reaction C02
H20
H2CO3, over the temperature
range 0-40"C. The values of k, were calculated from manometric determinations
of the rate of C02 uptake when gas mixtures containing suitable percentages
of C02 were shaken rapidly with phosphate or veronal buffers, pH 7-5-8.0.
In this pH range only slight corrections are necessary at low temperatures
for the velocity of the concurrent reaction C02 OH- -+ HC03- : above
20" C the corrections assume greater importance (see later). Pinsent and
Roughton 1 also measured manometrically the rate of C02 uptake by bicarbonate+
carbonate mixtures, pH 10-0-10.2, in which range the velocity of the reaction
C02+ OH--+HC03- predominates over that of the reaction C02+ H20+H2C03-.
From such data they were able to obtain values of k", as defined by the equation,

--f

- d[C02]/dt = k"[CO2][OH-]
(1)
over the temperature range 0-10"C. Higher temperatures were not feasible
for the manometric study of the C02 t OH- -+HCO3- reaction, since the
overall rate then becomes so much controlled by diffusion, that it is impossible
to apply sufficiently accurate corrections for the effects of the latter.
A few determinations of k" over the range 0-20" C have also been made by
the carbamino quenching method (Faurholt 2), by electrical conductivity measurements (Saal3) and by photo-colorimetry (Brinkman, Margaria and Roughton 4).
Generally speaking, however, the previous data on k" are either too restricted

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PINSENT, L. PEARSON AND F. J .

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ROUGHTON

1513

in number and temperature range, or insufficiently precise a n d there was clearly

scope for a n extended series of accurate determinations of k" over the range
0-40" C . T h e rapid thermal method of measuring the velocity of rapid reactions
i n solution (Roughton,s Bateman a n d Roughton,6 Roughton 7) seemed particularly suitable for this purpose, for in the interpretation of data obtained
thereby there is much less uncertainty as t o the effects of ionic strength t h a n is
the case in d a t a obtained by rapid electrical conductivity or photo-colorimetric
methods. Furthermore the rapid thermal measurement of k" provided a n excellent opportunity for extended tests of recently developed techniques (Pearson,
Pinsent a n d Roughton 8). In the present paper we have accordingly carried o u t
measurements, by the thermal method, of k" over a wide range of p H , salt concentration a n d temperature. Tn the appendix, concordant values of k" over the
range 20-30"C a r e derived from new manometric d a t a o n the rate of C02 uptake by
veronal buffers, p H 8.6-8.8. T h e results of the present paper are of physicochemical, biological a n d industrial interest : these varied aspects will each be
considered later in the discussion.
EXPERIMENTAL
The apparatus and general experimental technique have been described previously.
Details can be found elsewhere and only a brief resume will be given here.
The method consists essentially of driving the reacting solution through tubes into a
mixing chamber, from which the mixed solution flows along an observation tube of
length 10 cm and internal diameter 2 mm. The temperature of the flowing solution is
measured with a thermocouple at a number of known distances from the mixing chamber.
From the temperature rise the extent of the reaction can be calculated.
The bottles containing the solution, the mixing chamber and observation tube were
placed in a thermostat constant to 0.0015" C at 20" C and to 0.0025" C at 0" C and 40' C.
The solutions were driven through the chamber by nitrogen at a pressure of 25cm Hg.
Taps or clips were fitted so that either of the two solutions could be driven alone through
the mixing chamber or both together.
The thermocouple used in the observation tube was made from 30 gauge B.S.I. copper
and constantan wires with a single junction at the tip. This was calibrated with known
temperature differences, measured with a Beckmann thermometer. The thermocouple
was connected to a galvanometer with a period of 1 1 msec, constructed by Downing.9
The galvanometer deflection was further amplified by means of an optical lever and a
twin photocell in the way developed by Hill.10 The output of the amplifier was recorded
on a voltmeter.
The thermocouple and amplifier system gave an output of 9V/deg. A temperature
difference of 0.1" C gave a deflection of 75 to 80 divisions on the meter which was easily
readable to 3 division (approximately 0.0007" C). Each reading took at most 4 sec.
The system was calibrated with known voltages from a control unit.
MATERIALS.-&rbon
dioxide.-cO2 from a cylinder was bubbled into distilled water
in the storage bottle until the desired concentration of dissolved C02 was obtained. The
concentration of carbon dioxide was determined in a Van Slyke manometric apparatus.
Socliirrn hydroxide.-A saturated solution of A.R. sodium hydroxide was stored in an
air-tight plastic bottle. Small quantities of this stock solution were centrifuged and the
required quantity of the clear solution removed in a pipette and added to recently
boiled-out distilled water in a C02-free atmosphere.
Sodiw?i chloride: etc.-When experiments were carried out using solutions of high
salt content the salts were added in equal strength to both the carbon dioxide and the
hydroxide solutions, to avoid effects due to heat of dilution of the salts. Salts of A.R.
grade were used and the solutions made up as described above, using a salt solution in
boiled-out water in place of distilled water.
PROCEDURE.-The bottles n'ere filled with the solutions and the calorimeter placed
in the thermostat. I t was allowed to come into temperature equilibrium with occasional
stirring of the solutions. This took 1 h at 20" C and about 2 h at 0" C and 40" C. The
thermocouple was then placed in the observation tube and after a few minutes the recording system was calibrated with known currents from the galvanometer control unit.
Samples were withdrawn from the bottles for analysis.

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1514

C O M B I N A T I O N OF c02 WITH

OH-

The gas pressure was then applied and the thermocouple moved to the required
position. Readings of the meter were taken with (i) solution A running alone, (ii) both
solutions running, and (iii) solution B alone. The thermocouple was moved to the next
required position and the procedure repeated. Readings could be made at about 12
positions in the observation tube. At 20" C the readings for solution A and B running
alone remained nearly constant and were checked at only three or four positions. At
other temperatures more checks were made.
To determine the rate of flow the two bottles were marked with volume calibrations
and the volume of fluid flowing from the bottles in a certain time measured. This also
gave the relative delivery of the two bottles. The rate of flow was measured with the
thermocouple in several positions in the observation tube, as the rate varies slightly with
the position of the thermocouple (cp. table 1, Roughton 5). Knowing the diameter of
the observation tube, the time after mixing can be calculated at any distance from the
mixing chamber.
The temperature rise corresponding to each meter reading was calculated from the
temperature calibration of the thermocouple. Then at any point in the tube, if
temperature rise with solution A running alone
= TAY
temperature rise with solution B running alone
= TB,
temperature rise with both solutions running together = TM,
relative delivery of A to B :: 1 :x,
then the temperature rise due to the reaction
= TM - (TA xT~)/(l x).
If AH for the reaction is known the total temperature rise for the completed reaction can
be calculated and from this the extent of reaction at any time after mixing. If AH is
not known the total temperature rise for the completed reaction can be measured in the
apparatus with a suitable extension to the observation tube.

SCOPE AND ACCURACY OF METHOD

With the apparatus in its present form temperature readings were reproducible to
& 0 4 0 1 " C. The least total temperature rise practicable in order to obtain a reasonably
accurate figure for the velocity constant is thus about 0.025"C. The shortest elapsed
time at which reliable readings could be obtained was about 0.5 msec.
The thermal method has hitherto been tested and used with observation tubes of internal diameter 5 mm : it was therefore necessary to test the reliability of the present
apparatus, with its 2 mm observation tube, by means of control experiments similar to
those reported by Roughton.*
(i) Blank experiments with distilled water in both bottles gave no measurable
temperature change, i.e.,
TM - (TA x T B ) / ( ~ X ) 0*0007"C.
This shows that heat effects due to fluid friction and thermoelastic effects are
negligible.
(ii) The temperature rise when 0.0239 N HCl was mixed with 0.06 N NaOH was
determined in the apparatus and found to be 0165C. The expected temperature rise calculated from the heat of neutralization is 01635" C,showing that
heat losses from the observation tube are negligible.
(iii) Effects due to a " stagnant film " of liquid on the surface of the thermocouple
would be expected to be greater the slower the rate of flow of liquid. Experiments were carried out with the same concentration of reactants but varying
the rate of flow. Even with a two-fold variation in the linear rate of flow the
same temperature (& 0 4 0 1 " C) was recorded for any particular elapsed time at
any rate of flow.

+ >

RESULTS
The reaction followed was
C 0 2 OH- -+ HCO3OH- + CO32- H20.
(1)
At concentrations of OH- greater than 0.1 N all the bicarbonate ion formed can be considered to be transformed instantaneously to carbonate. At the lowest concentration

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B. R .

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PINSENT, L . PEARSON AND F. J.

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ROUGHTON

1515

of OH- used (0.0018 N) the error in assuming that all the bicarbonate is transformed to
carbonate is less than 5 % as long as only the first 50 % of the reaction is used for purposes
of calculation.
The heat change measured is the sum of the heat of the two reactions, and from this
the value of [CO32-], i.e. y , can be calculated. The velocity constant of the reaction
can then be calculated from the integrated form of eqn. (l), i.e.,

where a = [COz] at zero time, b = [NaOH] at zero time and kz" is the value of k" at
ionic strength I . Log [(b - 2y)/(a - y)] was plotted against t and the best straight line
drawn and the slope measured (fig. 1).
An extensive set of results was
obtained for kz" at 20" with [OH-]
1-3 rangingfrom 0.055 to 0.012 M, [COz]
from 0.013 to 04019 M, and the ionic
strength from 0.055 to 0.012. As
1.2
would be expected for a reaction, in
which a univalent anion reacts with
a neutral molecule, kI" is relatively
1.1
insensitive to ionic strength. Values n
x
of k" at zero ionic strength were obI
tained from kz" by means of the z 1.0data displayed in fig. 2. The largest N
n
%
correction was only about 3 %. The
variations in k" over the whole range QI 0.9of concentrations investigated were
2
within the experimental error of the 0.8
method thus confirming the validity
of the kinetic eqn. (2).
Table 1 gives values of k" over
the range 0"-40" C, the values at
temperatures other than 20" C being
the mean of 7 to 10 individual experiments in each case. These values
T i m e (msec)
were corrected for ionic strength,
assuming that the shape of the line FIG. 1.-Typical plot for determination of bilog kz"/Z was the same over the entire
molecular velocity constant kz".
temperature range. The corrections
are only about 2 % and so the errors involved in making this assumption were
negligible.
The effect of ionic strengths up to 5.0 was investigated by the addition of NaCl in
equal concentration to the C02 and NaOH solutions at 20C. Fig. 2 gives a plot of

._

W
U

TABLE VALUES OF THE VELOCITY CONSTANT

k" (M-1 sec-1) FROM 0"-40"C
temp.

"C

0
10
20
30
40

no. of
observations

7
8
27
10
9

k"
(mean)

1095
2550
5900
12400
24000

standard
deviation

53
87
315
835
3680

log kI" against ionic strength. The resulting curve converges very roughly to a straight
line given by the equation
log kz" = 3.77 0-26 I .
Although the slope of the line is uncertain the errors in using it for extrapolation at ionic
strengths below 0.06 must be negligible.
Table 2 shows the effect of addition of KCI, N a ~ C 0 3NaN03
,
and Na2S04 up to ionic
strengths of about 3.0. With sodium carbonate it was impossible to add the salt to the

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1516

C O M B I N A T I O N O F c02 W I T H

OH-

C02 solution and separate blank runs were carried out at each strength of Na2C03 to
determine the heat of dilution. A correction was made for the small bicarbonate content
of the sodium carbonate. The effects of KCl and Na2C03 are about the same as those
of NaCl at the same ionic strength : the effects of NaN03 and Na2S04, however, appear
to be somewhat smaller, due possibly to incomplete ionization of these salts in concentrated
solution (cp. Davies 11).

FIG. 2.-Relation
TABLE2.-vELOCITY

between velocity constant kz and ionic strength.

CONSTANTS IN CONCENTRATED SALT SOLUTIONS AT

20 c

tKCI1

[KOHI

[COZI

1.0

0.005 I2

2.0
3.0
3-0

0.0208
0.0134
0.0 196
0.02 15

0.004 12
0.00434
0.00457

1*02
2.01
3.02
3.02

9800
13700
17900
18200

2.0

[NaOH]
0.0244

0.00568

2.02

13700

0.0246
0.0244
0.0233
0.0288

0.00465
0.005 33
0.00635
0.00745

0.099
0.360
0.746
1.394

6280
6800
7800
10500

0.0203
0.0207

0.00438
0.00452

2.37
3.62

11 100
12400

0.0269
0.0203

0.005 19

I -53
3.02

10800

kz (M-1 sec-1)

[N~~COJI

0.0247 M
0.122 M
0.241 M
0.457 M
[NaNOJ

2-35
3-60
[Na2S041

0.5 M

1.0 M

0.00374

8700

Tables 3 and 4 give the measured heat of reaction of CO2 and OH- in the various salt
solutions. AH,b,. at high salt concentration will differ from the classical value of A H
in dilute solution, because the specificgravity and specific heat of the solution are no longer
unity. The heat of reaction in a number of these solutions was measured by allowing the
reaction to proceed to completion. It was found that the experimental results (AH,bs.)
agreed well with the values of A H calculated from the equation,

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B. R.

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PINSENT, L . PEARSON A N D F. J.

ROUGHTON

1517

where p = specific gravity of solution and s = specific heat of solution. The values
of A H are probably correct to & 5 %.
TABLE3.-HEAT

OF REACTION IN DILUTE
SOLUTIONS (cal)

AHobs.
- 20700
- 21200
- 22000

t"C
20"
30"
40"

AHCdC.

- 20580
- 20990
- 21270

TABLE
4.-HEAT

OF REACTIONS IN CONCENTRATED
SOLUTIONS AT 20"C (cal)

[NaCI]
0
0.86
2.00
3.00
5-00

AHobs.
- 20700
- 21150
- 21700
- 22100
- 22800

AHcalc.
- 20700
- 21250
- 21800
- 22000
- 22100

[KCII
2-00
3.00
4.00

- 22500
- 24000
- 25000

- 22700
- 23500
- 24300

DISCUSSION
COMPARISON WITH PREVIOUS DATA

The determination of k" at 0" and 18" C was first made accurately by Faurholt 2
with the aid of his dimethylamine quenching method. More recently Pinsent
I

10

20

30

40OC
I

PT
FIG. 3.-Temperature dependence of velocity constant k".
x = carbamino results
= manometric results.
0 = thermal results

and Roughton 1 have estimated k" at 0" and 10" C by means of their manometric
method, which-in the appendix-is extended by Meda to the temperature range
20-30" C . Fig. 3 gives a plot of log k" against 1/T for our thermal results from
0" to 40" C (open circles), together with the results of Faurholt adjusted to zero

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1518

OH-

C O M B I N A T I O N OF c02 W I T H

ionic strength (oblique crosses) and the manometric results (vertical crosses).
All the data conform satisfactorily to the equation,
log k" = 13.635 - (2895/T),
(5)
or
k" = A exp (- EJRT),
where A = 4 2 x 1013 and EA= 13,250 cal. The maximum divergence of any
point from this line corresponds to an error of only 11 %, which-considering
the precision of the various methods, their great variety and the wide range of
OH- concentration studied (- 10,OOO-fold)-is satisfactory.
Less extensive measurements of k" have also been reported by the electrical
conductivity method (Saal3) and by the optical method (Brinkman, Margaria
and Roughton4). Sirs,12 however, has recently brought to light a source of
systematic error in results by these two methods: when this is controlled the
estimations agree reasonably with eqn. (3, as will be shown in a paper to be
published by him later.
RECALCULATION OF THE VELOCITY CONSTANT

C02

k,

+ H20 + H2CO3

OF THE REACTION

Values of the velocity constant of the above reaction over the temperature
range 0-38" C were reported by Pinsent and Roughton.1 These results were obtained in phosphate buffer soluTemperature OC
tions at about pH 8.0,and were
corrected for the contribution of
the C02 OH- reaction, using
values of k" obtained by extrapolation of results from earlier
determinations of k".
These
values of k" were lower than the
present figures and this resulted
in the calculated values of k,
being too high, particularly at
higher temperatures. Corrections
have now been made using the
present accurate values of k",
and the corrected values for k,
are given in table 5 .
Fig. 4 gives a plot of log k,
against 1/T. The curvature is
YT
marked and the divergence from
FIG. 4.-Temperature dependence of velocity
the simple Arrhenius relationship
constant k,.
is greater than can be accounted
for by experimental errors. The apparent energy of activation varies from 19,000
cal at 0"C to 10,750 cal at 38" C ; the average value of dEA/dTover this range
is - 217. This is similar to the effects found in the reaction of methyl halides

TABLE
5.-vELOCITY
temp. ("C)
ku (=-1)

CONSTANT OF THE

0
040205

15
0.0112

c02 -k H20 -+ H2co3 REACTION

25

38

0-0257

0.0620

with water (Moelwyn-Hughes) 149 15 and other reactions such as the hydrolysis
of cane sugar. The falling-off of the apparent EA with temperature is found to
be most marked in reactions involving solute and solvent.
The temperature dependence can be expressed in the form
loglo k, = 329.850 - 110.541 log T - (17265*4/T)
(8)

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B. R . W . P I N S E N T , L . P E A R S O N A N D F . J . R O U G H T O N

1519

giving a true EA of 79,000 cal. This relationship has been used by MoelwynHughes14 to express the temperature dependence of the velocity constants of
the reaction
CH3X H20 CH30H H+ X-,
where X- is a halide ion. These gave values for true EA of about 47,000 cal.
Values of k, calculated from this relation agreed within 2 % with the experimental
values at every temperature.

BIOLOGICAL APPLICATION

In many biological fluids and cells the pH lies within the range 7.0 to 8.0
and the velocity of the reaction C02 OH- -+ HCO3- is therefore only about
3 to 30 % of the velocity of the reaction C02 H20 H2CO3 at body temperature, in absence of the enzyme, carbonic anhydrase. In the alkaline digestive
secretions, e.g. the pancreatic juice, the pH lies between 8-5 and 9.0 and in such
HCO3- reaction is 100 to 300 % of the
solutions the rate of the C02 OHuncatalyzed C02 H20 3 H2CO3 reaction and is thus of definite physiological
significance.

--f

--f

INDUSTRIAL APPLICATION

The rate of this reaction is a limiting factor in various industrial processes,

especially in the final stages of C02 absorption in the ammonia-soda process
for the manufacture of sodium bicarbonate. The conditions obtaining in such
processes are often outside-indeed
well outside-the
range covered in the
present paper, but the data herein nevertheless permit extrapolations to be made
with much greater accuracy than was hitherto possible in these cases. It should
be mentioned that the estimations at very high salt concentrations, recorded in
table 2, were specially designed for industrial application.
APPENDIX

k" AT 20" C TO 30" C

BY E. MEDA
The overall rate of reaction of CO2 in buffer solutions is given by the equation
MANOMETRIC DETERMINATIONS OF

- d[C02]/dt = V, = k,(l Im])[CO2] k"[CO2][OH-],

(A. 1)
where v, is the overall velocity of disappearance of C02, [B] is the concentration of the
more electronegativeconstituent of the buffer and I is the catalytic coefficient of the latter.
Between pH 8 and pH 10 both terms on the right-hand side of eqn. (A. 1) are important.
Pinsent and Roughton 1 have already determined k, manometrically over the range
0 to 40" C and have thence estimated k" from manometric experimentswith bicarbonate
carbonate buffers at pH 10 from 0" to 10" C. Higher temperatures were not feasible
since in this pH range the term [C02][OH-] then becomes so large that the overall rate
of C02 uptake becomes too much controlled by diffusion for corrections for the latter
to be satisfactorily made. By substituting veronal buffers at pH 8.6 to 8.7, however, it
has been possible to extend the temperature range to 20"-30" C, since at this pH the overall
reaction is about 10 times slower than at pH 10.
The technique adopted was the same as that used by Pinsent and Roughton.1 Sodium
veronate HCI buffers with a salt/acid ratio of 5 to 1 and total veronate concentration
ranging from 0.009 to 0.075 M were employed. Values of the overall velocity v, were
calculated for each veronate concentration and plotted against the latter. The points
fell satisfactorilyon straight lines, which when extrapolated to zero buffer concentrationgive
ku k"[OH-1. Subtraction of ku (see table 5) then gives k" [OH-] and thence k", if
[OH-] is known. The hydroxide ion concentration (at zero buffer concentration) was
calculated from the hydrogen ion concentration, which was in turn calculated from the
salt/acid ratio and the pK of veronal, as given by the accurate data of Manov, Schuelte
and Kirk 16 over the range 0" to 60" C. Table A1 summarizes the results obtained at
20", 25" and 30" C. These agree satisfactorily with those obtained in the main part of
the paper by the thermal method (see fig. 3).

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1520

HYDRAZINE FLAMES

TABLE
A MA MANOMETRIC VALUES OF k", 20"-30" C
k, in sec-1, k" in M-1 sec-1
temp. O C

PH

k, f k" [OH-]

k,

[OH-]

k"

20
25
30

8.75
8.68
8.61

0-0390
0.0668
0.1050

0.0 176

3.9 x 10-6
4.81 x 10-6
5.96 X 10-6

5,500
8,500
11,600

0.0257
0.0360

Acknowledgement is made to two of the Divisions of Messrs. Imperial Chemical

Industries for grants in support of this work.
1 Pinsent and Roughton, Trans. Faraday SOC.,1951, 47,
2 Faurholt, J. Chim. Phys., 1925, 21, 400.
3 Saal, Rec. trav. chim., 1928, 47, 264.

263.

Brinkman, Margaria and Roughton, Phil. Trans. A , 1933, 232, 65.

Roughton, Pruc. Roy. SOC.A , 1930, 126, 439, 470.
Bateman and Roughton, Biochem. J., 1935,24,2622, 2630.
Roughton, J. Amer. Chem. Suc., 1941, 63, 2930.
Pearson, Pinsent and Roughton, Faraday SOC.Discussions, 1954, 17, 141.
9Downing, J. Sci. Znstr., 1948, 25, 230.
10 Hill, J . Sci. Znstr., 1948, 25, 225.
11 Davies, J. Chem. SOC.,1938, 448, 2093.
12 Sirs, Ph.D. Thesis (Cambridge University, 1956).
13 Moelwyn-Hughes, Pruc. Roy. Sue. A , 1949, 196, 540.
14 Moelwyn-Hughes, Proc, Roy. SOC.A , 1938, 164,295.
15 Moelwyn-Hughes, Proc. Roy. SOC.A , 1953, 220, 386.
16 Manov, Schuelte and Kirk, J. Res. Nut. Bur. Stand., 1952, 48, 84.
4

5
6
7
8