KoY., l o r 6
I'HE J O L ' R N A L OF I . V D l . S T R I A L . I S D E.VG1.VEERING C I I 1 : ' M I S T K Y
gen salts of silver.' Sulfur fluoride docs not yield t o ultraviolct light (or visible light) although the sulf u r oxides and hydride are sensitivc t o ultraviolet light.z As Sheppard points o u t , t h e great stability of calcium fluoride is associated with a rcmarkable transparency t o ultraviolet light. Chlorine responds t o light chiefly in th.e blue, violet and ultraviolet. T h e absorption spectrum extends further into t h e ultraviolet t h a n t h a t of brominc3 I n this connection i t is of special interest t o note t h a t t h e photo:sensitiveness of silver chloride is apparently more marked in the ultraviolet t h a n silver bromide.' Bromine, in t h e free form, responds t o light less in t h e ultraviolet t h a n chlorine. On t h e other hand, hydrobromic acid is more easily decomposed b y ultraviolet light t h a n is hydrochloric acid. Iodine extends its spectrum still further towards t h e long wave lengths a n d hydriodic acid is decomposed b y ordinary blue and violet light. CONCLUSIONS
1035
on D. C. or a rcactancc coil in shunt around thc lamp reactancr coil and solenoid on A. C. IX--Finnlly, thcrc arc opcned up by the white flame arc, many new possibilities for controlling and changing chcmicnl rcaction. Light is a unique, uncontaminating, catalytic reagent for chemical reactions. We hope sufficicnt d a t a are here presentcd t o encourage others to take up thcse applications. A s Sheppard says a t the end of his book on photo-chcmistry, "We are only a t the beginning of the conscious utilization of t h e powers of light, as distinct from t h e unconscious enjoyment of them." RBSDARCIILADORA.IOP.IHS NATIONAL CARBONCOUPANY.CLIIYLILAND C.OODYBIRTias & Runeaa Co.. AYRON
THE MONOXIDE MONO RECORDER By P. D. H ~ a c z a Received September 12, 1916
I n a large number of industries where a definite knowledge of t h e percentages of carbon monoxide present in flue gases is of t h e utmost importance t o t h e manufacturing processes, such as chemical plants, cement, lime a n d brick plants, producer plants, etc., great need has been felt for an instrument which will automatically a n d continuously absorb and indicate as well as record t h e percentage of this gas. Such an instrument is shown in Fig. I. It is a combination COI and CO recorder and has lately been so improved t h a t b y the throwing over of a switch
I-The flame arc at high amperage is in proportion t o power taken, t h e most efficient known light source for photo-chemical reactions. 11-A single flame lamp can easily be made ten t o twenty times more powerful, as t o chemical effect, than any other single lamp except possibly t h e highamperage enclosed arc which at z j amperes on I I O line volts is about one-third as powerful as t h e flame arc at t h e same amperage. 111-The chemical action on solio paper by t h e light of t h e white flame arc through glass is nearly three times as powerful as t h a t of t h e other colored flame carbons under like conditions. IV-The chemical action on paraphenylenediamine (ultraviolet sensitive) b y t h e light of t h e white flame arc light through glass is also three times as powerful as t h a t of the other colored flame carbons. V-The white flame arc is the better suited for use with glass vessels which are cheaper t h a n t h e quartz vessels. VI-The direct current white flame arc has a photographic effect on solio paper t h a t can be expressed approximately b y t h e following empirical equation within t h e limits of moderate arc voltages (40 t o So). Photographic Power = KC1.8(V-z3) V = Arc Voltage C = Current K = a constant with a value of 0 . 0 0 8 j and an averPro. I age deviation of *0.0009. T h e standard of reference for this equation was photographic power on and a separate oxygen auxiliary also a continuous solio paper, which was called equal t o loo units at 25 analysis of oxygen can be readily obtained. T h e amperes and 6 j arc volts with a I I O volt direct current intricate value of such a n instrument, therefore, will be instantly appreciated. flame lamp which was used for making t h e tests. T h e principle of t h e apparatus is based on t h a t of VII-At high arc voltages the light and chemical power continue t o increase as t h e arc voltage is raised; the ordinary COI recorder which is known well enough t o need no description here. however, this is a t a decreasing rate. Fig. I shows t h e Mono CO? recorder in t h e center with VIII-A means of using a n enclosed arc lamp with flame carbons is here described. This consists in the filling device at t h e right-hand side and the monoxide using a shunt around t h e lamp resistance and solenoid auxiliary t o t h e left. This latter is connected with t h e CO, recorder b y means of n copper pipe of small diI See Sheppard. ''Photoehemlrfry.'' 8 . 315. 'See Berlhelot and Gnudcehon. Comnpl. r m d . , 186 ( I Y 1 3 ) . 1243-1245. ameter. I Sce Peskov. Lor. r i l . Fig. I1 is a general view of the monoxide auxiliary a See Bder'r "Hnndburh der Photographie,'' p. 292.
1036
T H E JOL’R.V:tL OF I , V U U S T R I A L A.VI) E.VGI.VEERI,VG
apparatus. A is t h e so-called dioxide filter, B the moisture regulator, which serves t o eliminate the condensation t h a t may have taken place in the pipelines and furthermore t o keep the gas entering the
CHEMISTRY
Vol, 8 , No.
11
into carbon dioxide, which then passes through t h e moisture regulator into the CO? recording apparatus where it becomes measured and the result is recorded CH, in the ordinary way. The record thus gives CO in percentages. Fig. I11 shows the design of the CO? recording instrument. Position 2 cuts out the auxiliary altogether excepting the moisture regulator. The electric oven thcn does not need to he in operation and. therefore, t h e left cock should hc on S. The gas passes directly t o the moisture regulator and from there t o t h e COS recording apparatus where the per cent of carbon dioxide is measured and directly recorded on t h e chart, which h a s a very widc rxnge, so that fractions of one pcr ccnt are plainly visible. Fig. I\‘ shows it reproduction of a chart taken from one of the instruments installed on board t h e S. S. Chrislioriafjord. The size shown is a little over a fifth of its actual sizc. (z\s :I matter of interest i t may he said hcrc that these instruments in this case arc suspended in unircrsal joints. making t h e same adaptable for marinc use.) The chart shows vcrp distinctly the c:irhon dioxide and carbon monoxide rcadings. Those showing about 1 1 per cent arerngc are the CO, records and those
+
2
.
.
?-
na. II recording instrument s~lwaysa t ii constant temperature. C is the electric oven for the oxidation of carbon monoxide and hydrocarhons. T h e cast iron hody of the apparatus serves t o cover and to protect the connections hetween t h e oven, the CO1 filter and the moisture regulator. Moreover it is provided with two cocks, one on t h e right and one on the left-hand side. These can he locked in t h e desired positions by lock and key of a very ingenious design. T h e left cock controls t h e current t o t h e electric oven and can he turned in two positions, T. for “on” and S. for “off.” T h e cock t o tlic right regulates t h e passage, which t h e gas, drawn in b y the rerorder, must t a k e according to what analysis is desired. This cock can he turned four ways: I , ? , 3 and 4. Position I is used for thc analysis of the unburnt gases; via., carbon monoxide and carbon hydrates. Inasmuch as the electric oven should he working at such time, the cock t o the left must he in Position T . The drawn-in gases then pass through t h e carbon dioxide filter,’ which is filled with a n absorbent, capable of completely absorbing all carbon dioxide contained in t h e gas. The remainder, i. e., carbon monoxide a n d carbon hydrates, passes into the electric oven where t h e heat in combination with another reagent causes t h e oxidation of the carhon monoxide and hydrocarhons
t
PIC
111
not exceeding the I pcr cent line are t h e CO records taken from the last pass of marine hoilcrs. Fig. V shows the recorder installed on ship hoard. Position 3 is used for checking the complete ah-
Nov., 1916
T H E JOC'R.V.IL OF I.VDC'SI'RI.1L . I S D E S G I . V E E R I N G C H E M I S T R Y
sorption of all cnrbon dioxide i n the CO? filter. This possibility of easy checking is of t h e utmost importancc because should this filter not absorb all CO? originally contained in the gas, t h e subsequent oxidation and measuring would be of no valuc as the result would not truly indicate t h c amount of CO therein. When the cock to the right is in this position the gas is first allowed to pass through t h e filter where i t is freed from all CO,. From there i t passes directly into t h e moisture regulator wherc i t is hrought t o t h e proper temperature and then it passes into t h e CO? recorder to be measured for CO?. If t h e filter has performed its
1037
plate so t h a t the saturation of the absorbent may he observed without disturbing the apparatus. T h e absorbent is originally colorless but bccomcs rcd as it absorbs Con,which color gradually spreads over the whole filter and remains as long as the absorbent retains its absorbing quality. .4s this latter diminishes, the original appearance of the absorbent is resumed. Thus the filter shows when it needs replenishing. The absorbent will last from one t o two weeks according to the numbcr of analyses desired and is re-charged with no more labor than is involreil in the winding of a clock. Position 4 is used for the checking of the pipc-lines for leaks. With this apparatus the analysis is made entirely automatically and at a rntc of up t o j o per hr. T h e correctness of the analyses is readily checked by t h e simple turning of a cock :is above described. Besides, t h e same instrument can he used for carbon dioridc as carbon monoside and if provided with a second auxiliary also for oxygen and should, therefore, find a great field in the various industries and power plants. The instrument as shown in Fig. 111 is adaptable for recording sulfur dioxide gas, only in this case t h e parts of the machine t h a t are coming in contact with the Rases within the machine. are made of special metal which will withstand their corrosive action. Either KOH or a n iodine solution is used as absorbent. 21
PARK
now. NBW
YORK
CITY
A NEW APPLICATION OF THE BUNSEN VALVE Ry ALAN I,EICIITON Heceived S e p t ~ m h c rIS. 1916
function properly, there should tic no COXleft and the recorder should score zero, which will be found t o be t h e case when the apparatus is in proper adjustment. By means of this operation one can satisfy oneself t h a t t h e gas, which passes t o the electric oven when t h e cock at the right is in Position I , is free from CO, a n d when after passing i t through t h e oven i t shows a certain amount of COI, this must have been caused b y t h e burning of t h e CO and CH, t o COI and can be relied upon as correct. The absorbent in the oven will last indefinitelv. T h e carbon dioxide filter is provided with a glass ~~
Everyone who has worked with suction pumps in t h e laboratory knows t h a t occasionally t h e water pressure goes off, the pump backs up, and t h e filtrate in t h e filter flask becomes contaminated. This can be prevented of course b y t h e use of a Woulfe bottle between the pump and t h e suction flask, but even this safety flask is not always :i safeguard, for it may become filled and overflow. This is particularly true if one is trying t o distill under a vacuum. I t would seem t h a t some simple valve could be constructed t h a t would prevent this danger. There are several such valves mentioned in the literature but they all have their limitations.' Since I A. Kunn. C h m . Zm.. ~. S I . 1136: Clwm. :lbs.. 1. No. 5 . S97; .&no".. Chrm. ZII., S4, 5 0 ; C h c n . Abr.. 8 , 2363: A. Berz, Bull. so
