ON T H E COEFFICIENTS O F ABSORPTION OF NITROGEN
`IX DISTILLED WATER AND SEA-
`AND OXYGEN
`WATER, AND O F ATI’dOSPHERIC CARBONIC ACID IN
`SEA-WATER.
`
`BY CHARLES J. J. FOX.
`
`The object of the present series of ineasureineiits was primarily the deter-
`mination of the absorption coefficients of nitrogen, oxygen, and atmospheric
`carbonic acid in sea-water. These coefficients have of late years acquired
`some special significance, notably in connection with that group of physical
`problems of which Arrhenius’s work on the diatherinancy of the atmospheric
`gases, particularly carbonic acid, and its effect upon terrestrial temperatures,
`is typical, and again in connection with those matters of biological interest
`which are concerned with the dynamic processes of pelagic life.
`In addi-
`tion, the absorption coefficients of nitrogen and oxygen in distilled water are
`not ltnown with great exactness, and it is believed that the present series of
`determinations will be of some interest from that point of view also.
`
`I. NITROGEN AND OXYGEN.
`The method employed for determining the absorption coefficients of
`nitrogen and oxygen is a modified form of Estreicher’s adaptation of
`Ostwald’s method.::: The gas is admitted to the burette A (Fig. I ) through
`the tube D ; its volume pressure and temperature are recorded. The bulb B
`containing the water freed from air is sealed on to the flexible glass spiral C,
`which is thereupon evacuated with a mercury pump and the tap c then
`closed. The volume between the three taps a, c, b is determined by allow-
`ing the gas to enter the spiral froin the burette and measuring the resulting
`decrease of gas in the burette. The tap 6 is next opencd and the bulb
`agitated until equilibrium between gas and liquid has been attained ; the
`the quantity of gas
`further contraction again resulting is a measure of
`absorbed by the volume of water taken, at the pressure and temperature
`observed. The pressure and temperature are then varied at will, and further
`measurements made upon the same quantity of water and gas.
`The object of the tube G in the present modification of the apparatus,
`which is in diameter and graduation identical with A,+ is to enable the
`measurements to be made at any pressure, within about 30 cm. around atmo-
`spheric pressure, instead of having to measure the volume of the gas always
`just in equilibrium with the water just at atmospheric pressure. Estreicher
`employcd the latter method, which is in practice by no means an easy thing
`to do exactly. The difference in mercury levels in the two tubes is, of
`course, a measure of the pressure at which the observation is made. The
`large beaker filled with water and fitted with a thermo-regulator serves as a
`* Estreicher, Zcit. fiir $liysiknl. Clieiiiic, 31, p. 176 ; Ostwald-Luther, Pl~ysiko-
`cliciiiische Aicssiiirgcrr, ate hufgabe, p. 274.
`t In linear inillimctres. The tube A was calibrated for volume by cutting it from
`the.rest of the appar;itus, sealing a tap on at the bottom, and then running out and
`weighing quantities of mercury in the usual way.
`68
`
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`Eton Ex. 1065
`1 of 19
`
`

`

`ABSORPTION OF NITROGEN AND OXYGEN
`
`69
`thermostat and allows il telescope to be used for reading off the volume,
`pressure and temperature. Precautions were taken to eliminate every possible
`parallax error, by adjusting levels, perpendiculars, &c.
`Estreicher, after having determined the volume and weight of the bulb,
`filled it with the water to be used (and a few C.C. of mercury to facilitate
`subsequent mixing with the gas), connected it directly by rubber tubing with
`an ordinary water-pump, and then boiled until about one-quarter of the
`water in the bulb had evaporated away ; the tap was at this point closed and
`the bulb weighed again. On now shaking the bulb the water hits the glass
`in the vacuum with the characteristic crackle. As a matter of fact, however,
`an exhaustive trial showed that it is riot possible to get coniplete evacuation
`
`7
`
`B
`
`in this way, and the sound alone is not a satisfactory criterion at all. If the
`bulb really were air-free, it would be found upon opening under a mercury
`surface that mercury would enter and fill it ; but a small residual bubble of
`air is invariably left, of volume about 0.01 to 0.10 C.C. at atmospheric pressure.
`It is difficult to get a water-pump to work quite evenly enough for this pur-
`pose ; the water in the bulb bumps badly even when it is warmed gently in a
`lukewarm water-bath ; a quantity of water condenses in the rubber tubing
`above, where it works up and down in effect like a piston, and this, no doubt,
`makes it difficult for the last traces of air to make their way out. It is suggested
`that Estreicher's values may be subject to an error on this account-in
`the
`case of argon of about 0'2 to 5 per cent., in the case of helium of 0.5 to 10 per
`
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`Eton Ex. 1065
`2 of 19
`
`

`

`70
`
`ABSORPTION OF NITROGEN AND OXYGEN
`
`rs 1
`
`cent. Winkler $: as a result of some theoretical considerations, which are,
`however, admittedly not quite conclusive, has also suspected that these
`helium values are not quite so reliable as are those accepted for some other
`gases.
`It is therefore to be hoped that these determinations will be repeated.
`In the present experiments the bulb was filled as follows (Fig. 2 ) : By
`means of a piece of thick-pressure tubing the bulb A was
`connected to the bulb B, and A and about one-third of B
`was then filled with the water. The water-pump was
`applied to the upper end of B, the water in both A and
`B was kept boiling for Io-Ij minutes ; A was then, of
`course, quite full of air-free water. But it is desirable that
`it should not be too full, and in practice about 10 C.C. of
`air-free space is convenient.
`It is easily adjusted at that
`or any other value by deflecting and inverting the bulb
`for a moment during the boiling so that a bubble of steam
`instead of rising to the water surface in B may upon
`formation collect inside A . When the bulb is filled with
`the water in this way no residual air will be found upon
`subsequently opening under a mercury surface ; and upon
`shaking, the water will be found to hit the glass in the
`vacuum with an intensity somewhat alarming, and much
`harder than is the case when the evacuation is carried out
`by the simple method adopted by Estreicher in his work.
`The nitrogen used in the determinations was obtained
`2.
`by several times passing air to and fro over warm white
`phosphorus,+ soda lime, and P,Oj ; the oxygen was generated by heating
`KMnO, in a tube, and passed over soda lime, and P,O,. All the apparatus
`was always evacuated and rinsed out with the gas several times before
`quantities for use in the actual measurements were finally collected in a
`glass gasholder,: which was also connected further to the mercury-pump and
`All joins were made with the blowpipe.
`the absorption apparatus.
`It is ne.cessary to ensure that the residual undissolved gas in the burette
`is measured saturated with moisture ; Estreicher ctttained this by so mani-
`pulatiiig the bulb and the mercury level in the burette, that a drop of water
`passed over through the spiral.
`In the present apparatus the same end was
`served more conveniently by filling the fine capillary tubing between the
`taps a and d with water, before sealing the tube E on to the gas-holder and
`mcrcury-pump. Then when the gas was admitted through d and n to the
`burette, this known quantity of water was swept in before it; all the
`ineasurements were made with the gas moist, and allowance was iiiade for
`the small quantity of water (about 0.015 c.c.), in calculating the results.
`A. D I STI LL ED 1i7"ATE K-NI TRO GE N .
`It must be noted here that to give values for pure nitrogen these measure-
`ments must be subjected to a correction dependent upon the fact that
`atmospheric nitrogen is a mixture of nitrogen and 1,18 j per cent. argon.
`The solubility of argon is inore than double that of nitrogen ; and the result
`is that, undcr the conditions of the present observations, the ratio of their
`partial pressures does not remain constant and equal to that found in the
`open free atmosphere, and it is diff erelit at differcnt temperatures.
`* L. W. \Vinkler, %rit.~frivpliysik. Clieniic, 55, p. 344.
`t Copper gauze was tried too, but it had to be reduced often, and the nitrogen
`prepared by passing over phosphorus gave quite the same values. After that had
`been established the inore convenient phosphorus was always used.
`As illustrated i n Travers, '' Experiinentelle Untersuchung von gasen," Fig. 121.
`
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`Eton Ex. 1065
`3 of 19
`
`

`

`W
`v
`
`M 23
`4
`*
`b <
`M
`r
`
`'I 1-33
`11-63
`I 2-3 I
`13.~2
`13-83
`'473
`15-76
`17'37
`I 8-90
`23.2 20.56 I
`
`_._
`
`(c.c. at oo 760).
`1,000 C.C. at lo 763
`Volrime Absorbed by
`
`1,noo a =
`
`1.402
`1.428
`I '480
`1.537
`1.578
`1.643
`1'697
`
`2.052
`2.238
`
`22-723
`22'505
`22.132
`2 1.675
`20.9%
`21.315
`20'662
`20.3 I 9
`19.916
`19'635
`19'250
`
`21'321
`21.077
`20'652
`20.138
`'9'537
`19.321
`18.965
`I 8.480
`I 8*002
`17'583
`17'012
`
`(10 700).
`Absorhcd
`Val iinic
`
`(c.c. at 1" ;Go).
`
`&is taken
`Volume of
`
`(C.C. at to 7Go).
`Unabsorbcd
`
`Volutre
`
`(Corrected).
`
`1'1-essure
`
`P=
`
`(c.c. at to#).
`Unabsorbcd
`
`Volumc
`
`(in c.c.).
`IZcacli ng
`Curettc
`
`'IP.
`
`PC'.!.
`
`t.
`
`Yoluiiic rciiiaiiiiiig in burcttc aflcr opening first tap (corrected) = 1q8495 at 9.p" and 788.3 tnm.
`Voluiiie of gas taken N, (corrcctcdj = 17.630 C.C. at 9.80~ aiid 857.95 mni. = 19.2124 at oo and 760 iiun.
`Yoluine of bulb empty at oo = 138.686 C.C. = v0,
`
`Voluiiic of water taken at 0" = 123'498 = w0.
`
`Voluiiic of spiral = 4.244 at y9oo = 4'243 at oo = 4.248 at 50°.:::
`
`:.
`
`AThIOSI'HERIC NITROGEN IN L)ISTILLED m'ATI.:R.
`
`Experiment I.
`
`t This observation was rejected ; it is affected by some exceptional error.
`* The cubical temperature cocfiicieiit of expansion of the glass used for the apparatus was found by experiinent to be o.ooooa3g between oo and 50".
`--
`
`63'700
`63.822
`63'680
`63'460
`63'020
`62'750
`6 I '489
`61 '550
`60.107
`60'100
`59.220
`Centimeti cs.
`
`25'438
`25.099
`24647
`24.1 17
`23.561
`23'401
`23'440
`22'818
`22.762
`22-235
`21.832
`
`7'277
`6.817
`6-1 13
`5'304
`4'559
`4'254
`4'184
`3'454
`3'330
`2.788
`2.410
`
`138.851
`I 38.841
`138'823
`138.802
`138786
`138.769
`138.754
`138.739
`138.719
`138.705
`138.689
`
`I 24,928
`124'807
`124.536
`I 24'236
`I 24.030
`123.857
`'23.732
`123.619
`123'53 1
`123.502
`I 23.5 10
`
`49-89
`46-79
`41-49
`34'99
`29.88
`24-90
`20.60
`15-72
`10'00
`6.00
`0'53
`
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`Eton Ex. 1065
`4 of 19
`
`

`

`ABSORPTION OF NITROGEN AND OXYGEN
`
`*.
`
`c
`
`p .
`
`>
`h
`
`i
`
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`Eton Ex. 1065
`5 of 19
`
`

`

`73
`IN GISTILLED WATER AND SEA-WATER
`If p and I - p be the partial pressures of argon and nitrogen in free
`atmospheric nitrogen ;
`if I, p,, p,, be respectively the total pressure and the partial pressures
`of the argon and nitrogen after solution equilibrium has been attained ;
`if a,, ax be the absorption coefficients for pure argon and pure iiitrogeii ;
`a be the coefficient actually found in these measurenients for the
`limited quantity of atmospheric nitrogen employed, and
`a' be the true corrected coefficient for free unlitriited atmospheric
`nit rogcn ;
`if v be the volume of water used in the bulb, and kv the volume of gas
`which remains undissolved, then-
`
`a = a,@, + asfs, and a' = QP + as ( I - $),
`+.a) + nx(1 -f -Ps).
`s = a ' - a = a * ( p
`But if after equilibrium is attained it is to be provided that nitrogen and
`argon still have the same ratio of partial pressures as they have in tlie
`atmosphere, theii-
`+a(/; + n.1)
`P
`f s ( k t ax) - 1 - p'
`f A + f x = I,
`
`and-
`
`and-
`
`(ctA--x)2(1
`
`whence by substitution it follows that-
`-rip
`.v = -+ ctA - p ( i A + pax'
`For atmospheric nitrogen p = o*o1185, and I -f = o.gS815.
`k of cour3e
`differed somewhat in the different experiments ; for present purposes, how-
`ever, it is sufficient to use always its mean value, 0.140.
`0.01 171 (aa - ctS)'
`:. .v = -~ 0.140 + o * ~ S S I
`j c t a + 0.01 1 8 j ~ s '
`This correction is always small ; for r,mo C.C. of water it is 0.1 C.C. nt o3 mid
`0.02 at 50'.
`Further, since-
`e l = a + .t'= o'gS815aN + o ' o I I S ~ ~ , ,
`a' - 0.01 1S5cc.1
`the absorption coefficient for pirre nitrogen = aN =
`o'g8S1 j
`The observatioiis (u) recorded above have been corrected accordinglp ;
`the interpolatioii formula for pure iiitrogeii theii calculated from them is-
`I , O O O ~ ~ = 22.998 - 0'529St + 0*0091~6i* - 0~0000677c)i3,
`and the values for each degree from oo to 50" are given in Table I.
`
`1
`
`2.
`
`I .
`
`I
`
`I
`
`3,
`
`TABLE I.
`
`4
`
`o
`I 0
`20
`j o
`40
`j0
`
`23-00
`18-54
`15-51
`13-5j
`12-15
`11'02
`
`22-50
`18.16
`I 5-29
`13-39
`I 2 '04
`-
`
`22'02
`17-80
`13.06
`15'23
`1 1 'y3 -
`
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`Eton Ex. 1065
`6 of 19
`
`

`

`74
`
`ABSORPTION OF NITROGEN AND OXYGEN
`
`Since the days of Bunsen's determinations, now only of historic interest,
`the absorption coefficients for nitrogen have been determined by Dittmar,:::
`Tornoe,+ Hamberg,: Pettersson and Sonden,$; but it is the determinations
`of Winkler 11 and of Bohr and Bock l T which are commonly regarded as the
`best values hitherto available. These determinations were evidently carried
`out with the utmost precision and care; but both were made prior to the
`discovery of argon. Winkler used atmospheric nitrogen and cmployed an
`apparatus theoretically analogous to that described here. The values pub-
`lished *::: must therefore be subjected to a correction in order to give values
`for pure nitrogen; his values refer to n and not to U' or uN. Bohr and
`Bock's values differ appreciably from those of Wiiikler and the present
`In making their determinations they usually bubbled a stream of
`writer.
`atmospheric nitrogen through water, and then estracted and measured the
`quantity of gas absorbed ; under these circumstances they must evidently
`have obtained not uN or a but a', and the values they have published, and
`which have since been copied into many works of refcrence, must therefore
`be corrected in order to give true values for argon-free nitrogen. (Argon is
`at oo 2.46 times and at soo 2.34 times as soluble as nitrogen.) Bohr and
`Bock's numbers must, therefore, be reduced accordingly in order to give
`values for pure nitrogen.
`Corrected in this way, it will be seen that Bohr and Bock's values are
`higher than Winkler's and Fox's until about 30°, above which Fox's are
`highest.
`
`1
`
`13-20
`13'5j
`13*j8
`
`11.6j
`12-15
`11.62
`
`1
`
`10.82
`11'02
`10.43
`
`...
`Wiiilrler ...
`...
`...
`Bohr and Rock ...
`FOX
`
`...
`...
`...
`
`23.14
`23-00
`23'47
`
`18.29
`18-54
`19-25
`
`
`
`-
`1
`-
`1
`-
`1.j*18
`I.j'j4
`16-13
`
`1
`
`I
`
`13. DISTILLED WATER-OXY GEN.
`The observations made in the case of distilled water and oxygen are
`shown in Experiiiieiits 111. and IV.
`The formula and values for 1,000~ from oo to so", calculated from these
`observations, are as follows (Table 11.)-
`1 , 0 0 0 ~ = 49'239 - I'3440t -(- O'287jZf'-
`TABLE 11.
`
`0'0003024f3.
`
`0.
`
`I .
`
`2.
`
`40.24
`38-37
`31'44
`26.6 j
`23 '30
`20'9 j
`
`47'94
`37'51
`30.91
`26-27
`2-3-02 -
`
`46 *65
`36-75
`30'38
`2 j'()O
`22'7 j -
`
`- I
`* Clcollcirficr* Expedition, Physics arrcl Cheniistry, vol. i., €3. 172.
`t Den Norske Nordhavs Expedition, 1876-1878, Chcinistry.
`$ Bihang ti1 K. Svenska, Vet. Akad. Hnirdliiqpr, 10, No. 13, 1885.
`$ Sveitsk Kwcisk 2'ici.slzriftl 1889, p. 17.
`11 \~'inkler, BEY. d. tlcritsclzcrc Chcnc. Gcs., 22 (1889)~ 1764 ; 24 (r891), 3602.
`71 Bohr and Bock, IVicclcrrictizn's Atciinlcii, 44 (1891), 316.
`** E$., Laiidolt and Bornstein's tables.
`
`-
`
`
`
`I
`
`-
`
`
`
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`Eton Ex. 1065
`7 of 19
`
`

`

`20.88
`20.88
`21'90
`21-95
`23-30
`23'32
`24-65
`24-65
`25.17
`35'19
`28-52
`28'47
`30'91
`31.05
`34.21
`33'97
`37'76
`37'75
`42-58
`42-58
`48'18
`48.6 I
`
`3.081
`3'538
`3'598
`3-46
`3'706
`3'204
`3'247
`3%
`3'319
`3'282
`3'522
`4'140
`3'784
`4'403
`4'725
`4.182
`5.060
`4'347
`4.152
`5'377
`5.1 10
`6'037
`
`28'193
`28'190
`27'757
`27'757
`27'304
`27'299
`20'9 I I
`26.903
`20.5 I 5
`26.509
`26.075
`26'075
`25.623
`25'622
`25.168
`25.168
`24.758
`24.751
`24'296
`24.288
`23.878
`23.861
`
`___-
`
`25'112
`24'652
`24.159
`24'6 I I
`23'598
`24.095
`23'664
`23'098
`22.696
`23.227
`22'553
`21.935
`2 2.839
`21'219
`20'443
`20'986
`IY'h.8
`20'404
`20'144
`18.911
`18.768
`17.824
`
`73'14
`83-99
`82.89
`72'30
`8 1.76
`70'62
`68-80
`
`Centimetrcs.
`
`69.16
`66-76
`78.62
`67'44
`78.1 2
`77'51
`69. I 2
`76'54
`65-77
`56'95
`73'51
`62.80
`73'57
`
`;::#
`
`26.094
`22.307
`22.151
`25'871
`2 I '936
`2.5'930
`26'140
`2 1'763
`2 I -446
`25.513
`25'673
`2 1.204
`24.6 I I
`20'643
`20.086
`23.075
`I9'559
`23'578
`20'882
`19'5.59
`22.713
`18'541
`
`I 1.806
`7'1 16
`7'607
`I 1,416
`7.127
`I 1.228
`I 1.23 I
`6-85 I
`6'359
`10.425
`10'416
`5.933
`0. I60
`5'242
`4'578
`7'467
`3'053
`89018
`I 1.285
`3'953
`6.142
`2'973
`
`138'85 4
`138.852
`138.836
`I 3 8.836
`138.8 19
`138.818
`I 38.805
`138.804
`138.790
`138'789
`138.773
`138'773
`138.755
`'38'755
`138.739
`I 38 "739
`138.723
`138.722
`138.707
`138.705
`I 38.690
`138.089
`
`129'527
`129'523
`129.242
`I 29.242
`128,970
`128.766
`128'756
`I 28.752
`I 28'562
`I 28.560
`128'375
`128.375
`128.213
`128.213
`I 28.088
`128.088
`128.014
`128.009
`127.967
`127.967
`127.975
`'27'976
`
`50'29
`50'25
`45'29
`45-20
`40'09
`40.04
`35'59
`35'49
`31'04
`30'98
`26-00
`26'00
`20'81
`20.80
`15-60
`15.60
`10-90
`10'82
`5-60
`5'57
`0.8 I
`0'6 I
`
`(c.c. at oo 760).
`I,COO C.C. at lo 760
`Voltinie Absorbed by
`
`1,OoO a =
`
`(10 760).
`Absorbed
`Voliinic
`
`(c.c. at lo 760).
`
`Gas 1;1 ken
`Volunie of
`
`(C.C. at to 700).
`Unabsorhcd
`
`Volume
`
`(Corrected).
`Prevsurc
`
`P=
`
`(C.C. at lop).
`Unabsorhcd
`
`Volume
`
`(in c.c.).
`Reading
`Burette
`
`Z't.
`
`U't.
`
`t.
`
`Yoluiiic rciiiaiiiiiig in burcttc after opening first tap (corrected) -= 16.293 at 15'43" and 903.7 mm.
`Voluiiie of gas taken 0, (corrcctcd) = 19.370 at 5.40' aiid 952-6 iiiiii. = 23.8078 at 0" aiid 760 iniii.
`Voluiiic of bulb ciiipty at oo = 138.686 = v0. Voluine of water takcii at oo = 127.9645 = w,.
`
`Voluiiie of spiral = 4'8580 at 15*43O= 4.5565 at oo = 4'8615 at 50".
`
`:.
`
`OXYGEX IN DISTILLED WATER.
`
`I I I I.
`
`E.v~l~rlllli~lI
`
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`Eton Ex. 1065
`8 of 19
`
`

`

`22-40
`22'41
`2406
`24-09
`26-60
`26.5 1.
`29'57
`29-67
`33'30
`33'44
`35'36
`35'50
`38-76
`38.76
`41-93
`41'89
`46.36
`47'27
`
`\'olume Absorbed by
`
`(C.C. at 00 70).
`I,COO C.C. at to 7Go
`
`1,000 CI =
`
`3'152
`3'667
`3'798
`3'318
`3'962
`3'447
`3'699
`4'343
`3'947
`4'623
`4'866
`4.218
`4'415
`5'1.52
`4'633
`5'421
`5'0Ii)
`5'928
`
`29.088
`29.085
`28.559
`28.587
`27'855
`27.853
`27'3%
`27'296
`26'647
`26.645
`26'372
`26.362
`25.991
`25'983
`25.714
`25'677
`25'308
`25'257
`
`25'936
`25'418
`24.76 t
`25.239
`23.883
`24'406
`23mGo6
`22'953
`22'700
`22'022
`22,506
`22'144
`2 1.576
`20.83 I
`21'081
`20.256
`20.289
`19'329
`
`.__
`
`(to 760).
`Absorbed
`Volume
`
`(c.c. at to 760).
`Gas taken
`Volume of
`
`(C.C. at fO 70).
`Unabsorbed
`
`Volu 111 c
`
`Ccntimctrcs.
`
`-
`
`71-59
`83-52
`82.23
`71-74
`70'74
`09'62
`68943
`80.1 I
`66'54
`77.61
`78-09
`67'45
`6j.61
`76.38
`64'88
`75'50
`04-06
`74'34
`
`(Corrected).
`
`Pressure
`
`f=
`
`27'534
`23.129
`22.719
`26.736:
`22-763
`26'643
`26.2 I 7
`21.775
`25'927
`2 1 '565
`2 I 904
`24'15 1
`24'992
`20'673
`24'694
`20'390
`24.07 I
`19.834
`___--
`(C.C. at t0P).
`Unabsorbed
`
`Voluwe
`
`12.395
`8,188
`5.53
`I 1.572
`7'204
`I 1.184
`10.569
`6' I 25
`10'1 I I
`5'750
`6.040
`8'086
`9'084
`4'766
`8.771
`4'468
`8'162
`3'930
`
`7'
`
`(in C.C.).
`ltcading
`Uu re t t e
`
`138.467
`I 38.466
`I 3 8.398
`138.397
`138.373
`138.372
`138.353
`138.351
`138.329
`138.328
`138.319
`138.318
`I 38-34
`138.304
`138.297
`138'293
`138.281
`138.278
`
`128'591
`I 28387
`128504
`128'303
`127'975
`127.974
`127.765
`127'762
`127.573
`127'573
`127'515
`127'513
`127.457
`127.456
`127.433
`127.430
`'27'429
`1 27'432
`
`43'29
`43'25
`37'54
`37.51
`2988
`29.86
`23.90
`23'80
`16'75
`I 6.72
`J3.75
`I 3.6;
`9'6 I
`9'53
`6-60
`6'20
`2-18
`1'63
`
`T't.
`
`PPt.
`
`i.
`
`Volume 1-einaining in burette aftcr opeiiiiig first tap (corrected) = 16.615 at 16-54' and 900.6 inin.
`Voluine of gas takcii 0, (corrected)=xc)g6j at 16.40' and 97.815 mm.=25*1071 at 0' and 760 mm.
`Volunie of bulb empty at oo= 138,2724 = 0,. Voluiiic of water takcii at oo = 127'4260 = wo.
`
`Yoluiiic of spiral= 5.060 at 16*54O=5*058 at oo=5*062 at 4j0.
`
`:.
`
`OXYGEN IS DISTILLED WATER.
`
`E.vfieriirtciif I V.
`
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`Eton Ex. 1065
`9 of 19
`
`

`

`IN DISTILLED WATER AND SEA-WATER
`
`77
`
`These values are intermediate between those of Winkler and Bohr and
`Bock.
`
`48'90
`49.24
`49.61
`
`I-
`
`26-08
`26.6 j
`2676
`
`i
`
`23.06
`23.30
`2326
`
`2090
`20.95
`2070
`
`::: 1
`
`...
`
`...
`'CG'iiikler ...
`...
`...
`Fox
`I30hr aiid Bock ...
`
`C. SEX-II'XTER.
`Before using the sea-water for filling into the bulb, it is necessary to add
`acid, otherwise it is .impossible to boil out all the carbonic acid or to prevent
`the precipitation of neutral carbonates. The very small quantity of acid
`which it is necessary to add was determined by heating 500 C.C. of the sea-
`water with excess of acid and then titrating back the excess, using phenol-
`phthalein as indicator. The chlorine was determined by titrating the water in
`the bulb after the absorption observations had been completed, by Mohr's
`method. The sea-waters used corresponded to about 7.5, 15, 20, and 23 per
`niille C1 respectively ; twenty-one duplicate observations were made in the
`case of each gas. The results were then combined with those given above
`for distilled water. The forniula for nitrogen gives the quantity of nitrogen
`and argon absorbed by sea-water from a free unlimited dry atmosphere in
`which the nitrogen always contains a constant percentage 1.185 of argon.
`(Dry air assumed to be 79.10 per cent. N, and 20.90 per cent. O,.)
`
`c1.
`
`0
`4
`8
`I2
`16
`20
`
`l-
`
`18-64
`17-77
`16-90
`16.03
`15-18
`I43 1
`
`17-02
`1627
`Ij'jC
`14'75
`14-00
`13-24
`
`I
`
`SO.
`
`I 5.63
`11-98
`1432
`13.66
`13-00
`12-34
`
`124
`
`IGO.
`
`200.
`
`240.
`
`280.
`
`14-43
`13.88
`13-30
`12.72
`12'1 j
`I 1- 57
`
`13-43
`12.94
`12-41
`11-93
`' 11-73
`10'92
`
`12.59
`12.1.;
`I 1-70
`11.25
`10-8 I
`10.36
`
`___-
`
`I 1-86
`I 1-46
`I 1-07
`I 0'67
`10'27
`9'87
`
`11'2-j
`10%g
`10' j 2
`1016
`9-80
`9'44
`
`TABLE IV.
`Xcmbcr of C.C. if Oxygen absorbed @I* 1,000 C.C. of Sca-zoatcr from n five dry Atmo-
`s~lzcrc of 760 iiiiii. Psessicre.
`1,OOO a = 10'291 - 0.2809f + OW06009t2 -/- 0.0000632t3
`- Cl(o.1161 - 0*003922t+ 0~0000631t~).
`
`C1.
`
`t = 00.
`
`4O.
`
`SO.
`
`0
`4
`8
`I 2
`16
`20
`
`10.29
`9-83
`936
`8-90
`8-43
`7'97
`
`9.26
`8.8 j
`8.4 j
`8-04
`7'64
`7'23
`
`8-40
`8-04
`7-68
`7'33
`6.97
`6-62
`
`7.68
`7.36
`7-04
`674
`6'43
`6.1 I
`
`I-
`
`l-
`
`I -__-
`
`7-08
`6-80
`6.52
`6-24
`5'96
`j.69
`
`280.
`
`5'75
`3'53
`3 3 I
`5-08
`486
`4-62
`
`6-14
`5.91
`5'47
`5'44
`5'20
`4'95
`
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`Eton Ex. 1065
`10 of 19
`
`

`

`78
`
`ABSORPTION OF NITROGEN AND OXYGEN
`
`2. CARBONIC ACID.
`As is well known, the analyses of the salts of sea-water show an excess of
`is to say, when the CO, is left out of account in such
`base over acid-that
`analyses. This CO, (about 50 C.C. per litre) is of course in equilibrium with
`the excess of base, which is actually cqual to about 40 nigrns. OH per litre.*
`It would seem that the partial pressure of CO, very seldom, or never, exceeds
`6 in TO,OOO, and the present work has been limited therefore to presstires of
`about I to 7 per ~o,ooo.f For the determination of the absorption coefficients
`of CO, there are consequently four independent variables to be considered ;
`that is to say, there is the influence of alkalinity, a chemical influence, in addi-
`tion to the purely physical influences of temperature pressure and salinity.
`The CO, dissolved may for convenience be regarded as made up of two
`parts ; namely, a small part, about I per cent. of the whole, dependent upon
`the physical influences alone, and therefore independent of the alkaiinity, and
`a far larger part dependent upoli the alkalinity pressure and temperature but
`independent of the salinity ; the saiictioii ior which arrangement will be found
`below.
`The small physical effect, which is also dependent upon temperature and
`pressure of course, may be calculated froin the measurements of Bohr on
`NaCl so1utions.f For p = I per 10,000 a is given for 1,000 C.C. of water in
`Table V., the values for other pressures being, of course, directly proportional
`is, equal to pa.
`to these values in accordance with Henry’s Law-that
`(C1 in
`grammes per mille, CO, in C.C. per litre.)
`
`-
`1. -
`
`~-I-
`
`TABLE V.
`
`10.
`
`14.
`
`20.
`
`0‘15j2
`0.1323
`01143
`0 ~ 0 1 9
`0.088y
`00807
`0075 I
`00630
`
`0.14s;
`0.1263
`0.1083
`O’Oy77
`0.0847
`00777
`00710
`0 0 ~ 0 0
`
`or621
`01383
`01203
`0’1061
`0093 I
`00837
`00752
`
`0‘1 jy8
`0 I 363
`0x193
`0.1047
`0’091 7
`0~0827
`0.0745
`00650
`
`0
`4
`8
`I2
`16
`20
`24
`28
`-
`There remains, then, to be considered the chemical effect of the alkalinity,
`and the methods employed in this work for the determinations involved were
`as follows-
`Chlorine was determined by titration with silver nitrate solution, with
`K,CrO, as indicator. The OH was determined in 200-500 C.C. by adding a
`known quantity of acid in excess, boiling off the CO,, and then titrating the
`excess of acid with standard alkali, using phenolphthalein as indicator. The
`CO, pressure was determined by Pettenkofer’s method, modified to suit the
`present requirements.
`In this method a known quantity of Ba(OH), solution
`is added to a bottle of known capacity, filled with the air to be analysed for
`CO,, and the excess of Ba(OH), is titrated after all the CO, has been absorbed
`and precipitated as BaCO,. The chief source of error in this method seems
`* Dittmar and also Tornije always gave this excess of base over acid, or alkalinity
`as they called it, in terms of the unnecessarily cryptic unit of quantity of CO, neces-
`sary to convert it into normal carbonate ; and, unfortunately as it would seem, this
`practice has been followed ever since. The unit used here will, however, be gms.
`or mgins. OH per litre ; the factor for transforming data published hitherto into
`gms. OH per litre is o.oorg17.
`t See Krogh, Illctlrleldser oiit Gribilatid, Heft 617, 33 1-434.
`Bohr, Aiiii. der Pltys. 11. Cltciit., 62 (1897), 614.
`
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`Eton Ex. 1065
`11 of 19
`
`

`

`IN DISTILLED WATER AND SEA\-WATER
`
`79
`
`JWW-O
`
`FIG. 3.
`
`to be the action of the Ba(OH), on the glass, and a number of bottles
`(8-20 litres) of different glasses were examined from this point of view.
`Most of the measurements here recorded were carried out with two bottles
`(12 litres) of Jena Gerate glass, which were
`found quite satisfactory. The measure-
`ments were therefore carried out as follows :
`500 C.C. of sea-water was put into the bottle,
`which was then rotated by means of a
`motor, with its axis horizontal (Fig. 3),
`until the water was in equilibrium with
`the air above it. In this arrangement a thin
`film of water is carried round, adhering to the walls of the bottle in rotation,
`If
`which is continuously renewed ; equilibrium thus takes place quickly.
`the CO, pressure required was that of the atmosphere, a current of air was
`drawn through the bottle during rotation with an ordinary filter-pump. If
`any other pressure was required thc bottle was merely closed instead with a
`rubber stopper carrying two glass tubes (Fig. 4), which allowed the water to
`be drawn off after equilibrium had been obtained and then
`Ba(OH), solution to be added without disturbing the air inside.*
`In this latter case, too, it is neccssary to add BaCI, solution
`as well as Ba(OH), in order to prevent the NaCl contained
`in the drops of water which still remain hanging to the walls
`of the bottle, after as much as possible has been run out,
`from reacting with the precipitated BaCO, ; this would spoil
`the end point of
`the titration with standard acid and
`phenolphthalein. The excess Ba(OH), was titrated as quickly
`as possible with standard succinic acid while still in the bottle,
`and the stopper was not removed until near the end point.
`The sea-water run out was analysed for total CO, (and OH)
`in the apparatus illustrated in Fig. 5, which the writer has
`used some years for extracting gases from liquids, and which
`has proved very convenient for the purpose. The sample
`of liquid for analysis, if sealed up in a tube, is admitted by
`way of c ; if in an open vessel it is drawn into the evacuated
`FIG. 4.
`flask by way of a ;. the quantity of water drawn in is
`determined by weighing the vessel before and after the water is admitted.
`A known quantity of standard acid is admitted through H , and after all the
`gases have been extracted the water is withdrawn, with the help of a filter-
`pump, into another empty flask by way of a again, and a titration of the
`excess of acid then gives a determination of the total alkalinity.
`Before the water sample and acid are admitted to the apparatus, the flask
`A is evacuated by boiling in it some distilled water, by exhausting siniul-
`taneously with a filter pump applied at I , and finally with the mercury pump
`B, and by also washing out with an indifferent gas (usually hydrogen) gene-
`rated in the pipette C and admitted by the tap I1 as required, A very
`efficient condenser is necessary owing to the low temperature of boiling, and
`the form known as Cribb’s is very well suited to the purpose, especially as it
`takes up so little room. After the apparatus has been freed from air in this
`way, the sample to be analysed is admitted together with the acid, the gases
`* In calculating p, it is necessary to apply a correction for the quantity of air
`which displaces the water as it runs out, and also for the CO, contained in the
`small quantity of water which remains behind adhering to the glass. A series of
`tests showed that these two corrections together could be kept down to about
`5 per cent. of $.
`
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`Eton Ex. 1065
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`
`

`

`80
`
`ABSORPTION O F NITROGEN AND OXYGEN
`
`estracted are collected in B and transferred by way of b, d to the burette D
`for analysis ; finally, the last traces are washed out with the indifferent gas
`from the pipette and also added. In the case of sea-water the mixture of
`CO,, N,, 0,, and H, thus obtained is analysed by absorbing first the CO, in
`the KOH pipette E, then exploding the 0, with the H,, which must bc in
`excess, and finally the excess of H, (and consequently thc 0, by difference}
`in the mixture then remaining, by adding a measured escess of 0, and
`esploding again. 0, for this purpose is generated by heating KMnO, con-
`tained in the tube G, and it is collected in the pipette F for use as 1-cquired ;
`whence it may be transferred to the burette in small quantities at a time by
`help of the pump. The apparatus is very easy to keep in working order, aiicl
`is capable of giving very accurate results. The only precautions necessary
`are to wash out the burette with a drop of dilute acid kept for the purpose
`QII the top of the mercury in the cup of the KOH pipette, in case a bubble of
`KOH should have been carried into the burette in the preceding analysis ;
`
`Fro. 5.
`and to pay attention to the risk of exploding a mixture of H, and 0, in too
`great proportion to the N, present, which is apt to cause the formation of
`nitrous acid, and to avoid which it is necessary and sufficient to use only
`small quantities of hydroge