July, 1925 I.

\-DUSTRIAL AAVD EXGINEERING CHEMISTRY 745

The results of the analyses are given in Table I, and it is
seen that (1) no appreciable loss of calcium results through
the use of persulfate, and ( 2 ) there is no serious contamina-
tion of the lime or magnesia by manganese.
The behavior of uranium, titanium, and vanadium under
these conditions was also tested as follows: Solutions were
prepared containing about 0.15 gram Fe203 to which were
added in the first series 0.005 gram of VZOS;in the second
series 0.005 gram of TiOz; and in the third series 0.005
gram of [TO3. After precipitation made by the method given
above, the filtrates showed no trace of titanium or uranium
and only a very faint trace of vanadium. Apparently,
under these conditions the presence of persulfate had no dis-
turbing action on the precipitation of these elements by am-
monia. Chromium, if present, will be found in the filtrates
and may be removed before the precipitation of calcium.3
It is believed that this modification of the Blum method
will be found simple in manipulation, and it is evident from the
foregoing results that it is satisfactory for the precipitation
of manganese in the ammonia precipitate, and for the elimi-
nation of its interference in the determination of lime and
magnesia.

Solubilities of Sulfur Dioxide and Ammonia in Water’

By T. K. Sherwood

XASSACHUSETTS OP TECHNOLOGY,
INSTITUTE CAMBRIDGE,
MASS,

experimental points on such a plot drawn to a large scale.

Those figures in parentheses are from extrapolated portions
of the curves, shown dotted on the plot.
Table I-Solubility of Sulfur Dioxide in W a t e r

SOLUBILITY OF SO, IN W4TLR

water are not included
as they were evidently
I2 from the same sources,
and check excellently
11
5 those given by Zeis-
10 berg2 in r‘t recent ar-
d 9 ticle.
3 I n the treatment of
ga 7e the data on the solu- c,
0
a. bility of sulfur dioxide, SOLUBILITY OF SO, IN WATER
I
~6
R it is assumed that the
6 5 dissociation is constant
3 4 a t any particular tem-
3 p e r a t u r e , and that 200
Henry’s law applies to
2
t h e undissociated
I solute. On the basis of
0
5 10
Is x) ~,
these assumptions it
P4RTUL PRESSURE 5oeM M Hy. has been shown3 that vi IS0
I
s = H,b m+ p 0

or sit’s = Hd; +
C H 0
where s
p
H
= grams SO2 dissolved in 1000 grams water
= partial pressure SO*, mm. mercury
Henry’s law constant
:
K
=
= dissociation constant of t h e HpSOs ::
N
100

vi
5
Therefore, the data were collected in the form of a plot of
.s/dFversus dF
The best straight line was drawn through
the points on this plot, and the curve and Table I of s versus
p are from points taken from this line. 50
The data on the solubility of ammonia have been plotted
on logarithmic paper to reduce the curvature of the resulting
line, and to obtain a constant percentage error in plotting.
The data in Table I1 are from the best line through the
1 Received March 26, 1925.
2 Chem. M e t Eng , 32, 326 (1926).
PARTIAL PRESSURE SO2 M.M. Hq.
8 Haslam, Hershey. and Keen, THISJ O U R X ~ L ,16, 1226 (1924).
746 I S D U S T R I A L ,450 ESGIAVEERISG CHEMISTRY 1-01. 17, Xo. 7

p - PARTIAL PRESSURE NH, IN M.M. MERCURY

T a b l e 11-Solubility of A m m o n i a i n W a t e r Acknowledgment
Grams
?;Hq/1000 Thanks are due C. E. Lanyon, W. K. Lewis, and R. G.
grams PARTIAL XHa, MM.H
PRESSURE G
-
-
water ‘00 c 100 c 200 c 300 c 400 C , 500 C , 600 C, Whitman for references and suggestions.
1000 94!
900
800
is5
636 987
Bibliography
700 500 780 S o l u b i l i t y of Sulfur Dioxide
600 380 600 943
500 2ij 439 686 1-Scbonfeld, A n n . , 96, 1 (1853).
400 190 301 470 719
300 119 190 298 434 692 C-Sims, Ibid., 118, 340 (1861).
250 S9.5 144 227 352 534 825 3-Roozeboom, Rec. trau. chim.,3, 29 (1884).
200 64 103.5 166 260 393 596 S34 4-Lindner, Monafsh., 33, 646 (1912).
150 42.7 iO.l 114 179 273 405 5S3
103 25.1 41.8 69.6 110 167 247 361 j-Freeze, Wochbl. Papierfabr., 51, 861 (1920).
(0 17.7 29.9 50.0 79.7 120 179 261 6-Smith and Parkhurst, on file, M. I. T. Research Laboratory of
50 11.2 19.1 31.7 51.0 76.5 115 165 Applied Chemistry.
40 16.1 24.9 40.1 60.8 91.1 129.2
30 11 3 18.2 29.6 45 67.1 94.3 7-Watts, J . Chem. Soc. (London),2, 88 (1864).
25 l5,O 24.4 (37.6) (55.7) 77 S o l u b i l i t y of A m m o n i a
20 12.0 19.3 (30.0) (44.5) 61
16 15.3 (24.1) (35,s) 48.7 I-Raoult, A n n . chim. phys., 1, 262 (1874).
12 11.5 (18.3) (26.7) 36.3
10 (15.4) (22.2) 30.2 2-Carius, A n n . , 99, 144 11856).
July, 1923 I-\\'DCSTRIdL d S D E-17GISEERIA17G
CHEJIISTRY 717
3-Perman, J . C h o n . SOL.(London), 83, 1168 (19031. 8-Mallet, A m . Chem. J . , 19, 807 (1897).
4-Watts, I b i d , 2, 88 (1864). 9-Mollier, Milt. Forschungsarbeifen, 1909, Heft 63-64,
5-Sims, A n n . , 118, 345 (1861) 10-Smits and Postma, Verslag. .-lkad. TT7efenshnppen, 23, l l i (1914).
6-Roscoe and Dittmar, I b i d . , 112, 349 (1859). 11-Doyer, Z . p h y s . C h e m . , 6 , 486 (1890).
7--Cragoe, Myers, and Taylor, J . A m . Chem. Soc.., 42, 220 (1920). K-Gaus, Z. anorg. Chem., 26, 236 (1900).

Rectifying Column Calculations'

With Particular Reference to N Component Mixtures
By E. V. Murphree

THESOLVAY
PROCESS
Co., SYRACVSE,
h7.E'.

calculation simplifications viewpoint,

this is the method generally Rectification consists es-
The concept of the theoretical plate does not offer a
used today.3 Lewis' has sentially in the trarlsfer of
an approximate satisfactory basis of calculation for rectifying columns material between a gas
method of calculation for when the mixture being rectified contains more than
phase and a liquid phase.
cases ill Tvhich the rate of ' two components, and even for some calculations on
binary mixtures its use is not satisfactory.
I t is therefore a special case
change of compositioll of the ' o f a b s o r p t i o n . The leas
A method of calculation for actual plates which can
liquor from plate to plate of volatile components are ah-
ideal is be used for mixtures of any number of components
l sorbed and the more volatile
His method considerably is developed from the absorption equations.
' liberated. The equations
simplifies the calculations. A means of expressing the efficiencies of rectifica-
j
tion of the volatile components is given.
1
for the rates of material
It should only be used, transfer are of the following
however. when the rate of 1 type?
change is small.
I n actual columns, equilibrium between vapor and liquor is
seldom realized, and consequently the number of plates needed
to perform a given separation in a n actual column is usually where 8R' = time of contact of liquor and vapor
= quantity of component one transferred to gas phase
greater than the number calculated for the ideal column. The for a n area of contact of A
ratio of the number of ideal plates to actual plates or the num- k , = conductivity of gas film for component one
ber of ideal plates equivalent to one actual plate for a given k , = conductivity of liquid film for component one
column is called the plate efficiency of that column. This i> d = area of contact of liquid and vauor
a n average value.
P, = partial pressure of component &e a t vapor-liquid
interface
The plate efficiency for many cases gives a satisfactory P, = partial pressure of component one in main body of
basis for the comparison and design of fractionating column;. gas
I t is probably a function of several variables, the most inipor- CL = concentration of component one in main body of
liquid
tant of which seem to be the type of plate, the substances be- C, = concentration of component one a t vapor-liquid
ing fractionated, and in some cases the temperature. Pe- interface
ters5 first showed the variation of plate efficiency with the
material being separated. The author has seen tests on a K h e n the liquid film resistance is negligible in comparison
given type of column which gave plate efficiencies varying with the gas film resistance or when the partial pressure is a
from less than 0.1 up to 0.8, depending on the particular linear function of the concentration, Equation 1 reduces to:
substances being fractionated. dll'
_
de - Ku "I ( P L - Pd
I n certain types of rectification the concept of the ideal (2)
column does not offer a satisfactory basis of talculation. where K , = a n over-all conductivity for component one
P L = partial pressure of component one in equilibrium
K h e n the plate efficiency is small, it is rather unsatisfactory with liquid
not to be able to trace the liquor from plate to plate of the
actual column. This is especially true when liquor or vapor is For cases in which the gas film resistance is negligible in coni-
added or withdrawn from the column on other than the ternii- parison with the liquid film resistance Equation 1 reduces to
1 Recelled March 19, 1925
. -
La Rectification de I Alcool. ' 1893, Parr,
3 Lewis THISJ O U R ~ A L 1 , 522 (1909)
where K , = a n over-all conductivity for component one
* Ibrd , 14, 492 (1922) C, = concentration of liquid in equilibrium with the vapor
a / b i d 14, 476 (1921) 8 Leais a n d Whitman, THISJ O V R N A L , 16, 12i.5 (1924).