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The viscosity of pure hydrogen bromide and solutions of ecetic acid and ethyl alcohol in hydrogen bromide Banfield, William Orson 1923

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MBjmcarrr.: cr;. - - * * « * ' THE VISCOSITY of PURE HYDROGEN Vv Aft'.'wrf!..': . ' BROMIDE and SOLUTIONS of  ACETIC and ETHYL ALCOHOL in HYDROGREN BROMIDE by WILLIAM ORSON BANFIELD UNIVERSITY OF BRITISH COLUMBIA. THE VISCOSITY OF PURS HYDROGEN BROMIDE AND SOLUTIONS OF ACETIC ACID AND ETHYL ALCOHOL IN HYDROGEN BROMIDE. BY WILLIAM ORSON BANFI3LD. A THESIS SUBMITTED FOR THE DEGREE OF MASTER OF APPLIED SCIENCE IN THE DEPARTMENT OF CHEMISTRY, THE UNIVERSITY OF BBITISH COLUMBIA. April 1923. CONTENTS. Page, Introductory 1 Relations of Viscosity to other physioal characteristics of liquids 4 Methods of measuring viscosity 6 Calibration of viscometer 9 Preparation of Hydrogen Bromid e 9 Visoosity of Pure Hydrogen Bromide: Apparatus 1 2 Mode of Procedure 1 3 Results of Teats—Table I 1 4 Discussion of Results 1 6 Visoosity of Solutions of Aoetio Acid in hydrogen bromide: Apparatus 1 7 Mode of Procedure 1 7 Results of Tests—Table II 1 9 Discussion of Results 2 3 Visoosity of Solutions of Ethyl Alcohol in hydrogen bromide: Apparatus 2 4 Mode of Procedure 2 5 Results of Tests—Table III 2 7 Discussion of Results 3 2 Conclusion 3 3 Summary 3 3 THE VISCOSITY OF ^ UKS BTOROGEU BROMIDE AND SOIUTIONS OF AOBTIO AOID AND ETHYL ALOOHOL IN HYDROSEN BROMIDE. INTRODUCTORY. The measurement of the flow of liquids in oapillary spaces was not made until after the fundamental laws of Hydrodynamios were established by suoh men as Bernouilli (1726), Euler (1756), Proury (1804), Novier (1823), and Poisson (1831) . Otherts later studied the flow of liquids in tubes of large bore but it remained for Poiseuille in 1842 to lay before us the simple nature of the flow of liquids in oapillary spaces. Hi s interest in oapillary flow was prompted by an interest in the flow of blood in the oapillaries. H e made a great many measurements on the rates of flow of liquids through oapillary tubes and evolved a law whioh bears his name and which describes the effeot whioh the size of capillary, length of capillary, pressure causing the flow, temperature of the liquid and the resistance to slipping of the moleoules of the liquid, have on the rate of flow of the liquid. This law which is known as the "law of Poiseville takes the form _., . n *~. Inhere Y =  tota l volume of efflux 77* =  s . 14159 G =  Forc e of gravity P =  Pressur e E •  Diamete r of Capillary T Tim e of flow, of volume. L "  Lengt h of Capillary V -  Ge/J. o f viscosity of the liquid The usual faotor which it is desired to measure is N the coefficient of viscosity and the equation takes the form L 3  LV Maxwell, who along with Hagen , Wiedeman, Hagenhaok, and Helmholta, supplied the theoretioal basis ffer the laws of viscosity defines viscosity as "The visoosity of a substance is measured by the tangential force, on a unit area of either of two horizontal planes at unit distance apart, required to move one plane with regard to the other at unit velocity, the space between feeing filled with the viscious substance. Later investigators as Veumanu (1858|, and Jaoobson (1860) sought to acoount for the kinetic energy whioh the liquid had on leaving the tube* • 3 -This wa s pu t int o a  s a t i s f ac to r y for m whio h i s where M  •  =  A  constan t =  1.1 2 /° = • dens i t y o f th e l i q u i d the othe r fac tor s hav e value s a s before . This Kineti c energ y correc t io n wa s substraote d fro m the valu e o f \  give n above . The valu e o f th e constan t "M " ha s bee n th e cause o f a  grea t dea l o f inves t iga t io n an d controversy bu t th e valu e give n abov e i s no w pr*t y general ly acoopted . ( • } 4 The methods of measuring visoosity are many and new ones intended to give better values are oonstantly being developed, so that absolute visoosities may be determined in a number of ways. Ther e are some procedures which follow the method used by Pojseuille, and which measure relative visoosities only, but are susoeptible of mathematical treatment to enable absolute visoosities to be obtained, RELATIONS OF VISCOSITY TO OTHER PHYSICAL gHARACTgRlSTIOS 0? 11GUTD51 It was considered by a number of investigators that the visoosities of mixtures were additive, but (1904), Dunstan/pointed out that suoh was scaroely the case. He states: "The law of mixtures is never accurately obeyed an d divergences from it seems to be more clearly marked in the case of visoosity than in other physioal properties." Also Thorpe and Rodger earlier C1897) , state that, w Th e visoosity of misoible and ohemioally indifferent liquids is rarely, if ever, under all oonditionB a linear function of the composition." Th e knowledge ot visoosity of a substance will aften give important results in the study of its other physioal properties, of whioh, oonduotanoe, composition, rate of diffusion and vapor pressure, are but a few of the most important, and whioh have been studied more or less exhaustiTely. (E.C. Bingham, Fluidity and Plastioity, Mo Garaw Hill New York 192£, Chapters 1 to 5, Part 11.) •fr-it was in an endeavor to assist in solving the question of the relation of viscosity to other physioal properties that the following measurements were oarried out* -6 METHODS OF MEASURING VISCOSITY. The form of viscometer used for these tests was that of Ostwald, which oonsists essentially of a vertical oapillary about 10,5 cm long and of a 4 mm bore at the top of which is a small bulb of a capacity of B«l cubic cm and at the bottom is a large tube of a U shape oonneoting the oapillary tube to a larger bulb which is surmounted by a large tube. Figur e I shows the shape of the viscometer and comparative sizes of its parts. The mode of procedure oonsists of inserting the same volume of the ligjaid to be measured into the lower bulb and then hlowing or sucking it until it rises beyond the mark above the upper bulb. The n the liquid is allowed to fall under its own weight and the time the min^ous takes to fall between the marks above and below the upper bulb is noted and taken as the time of flow* The tube is calibrated with water at 20° centigrad e at which temperature it has a visoosity of .01005, The use of such a method for obtaining values of visoosity simplifies the work greatly beoauae the measurement of volume of flow and dimensions of the oapillary which are demanded by the formula of Poiseuille and the ktnetio energy correction can be grouped together under oonstants for the particular tube. Th e formula then becomes lS^CPT-k //j~ -7-The measurements obtained this way are relative only but by the seleotion of a suitable liquid as a standard the advantage of expressing visoosities in absolute units as well as relative to some standard may be had if water at £0 degree s oentigrade i e usedtalso if the abeolute unit of visoosity is called a Poise, and the submultiple is oalled a "Centipoise", whioh is one one-hundredth as large. W e get as the value of the oentipoise in this ease 1.005 whioh is 1 within limits of expealnsrttal error. Heno e absolute visoosities expressed in oentipoises are also specifio visoosities referred to water at 20 degrees centigrade. The formula then for the viscometer will be where \ D i s viscosity of the standard liquid and E is visoosity of liquid to be measured. If the \ &  T^ , are nearly equal the formula may be written a .  PT ho ex and as ia this viscometer the pressures are proportional to the density the formula then becomes n _  /°r If the visoosity is expressed in oentipoises -8-1. =7,< . # - r T The values of visoosity given in the following results are therefore given in oentipoises. -9 CALIBRATION OF VISCOMETER^  The referenoe liquid used for the calibration of the viscosity tube was water. The tube was first carefully oleaned then filled to a fixed level in bulb Z, Fig. I, with distilled water, and it was immersed to within a oentimeter of the top in a oonstant temperature bath maintained at 20" centigrade, and after the tube had assumed the temperature of the bath, readings of the time of flow were taken. A  stop watch reading to hundredths of a minute was used to indicate the time; a third figure could be oorreotly estimated. A t least ten readings were taken, then tube was again washed out, refilled and another set of ten readings taken. Th e average of these gave the time of flow for the tube for water* THE PREPARATION OF THE HYDROGEN BROMIDE. The hydrogen bromide was prepared by the action of liquid bromine on red phosphorus, in the presence of water. The reaotion is essentially 3 Br  +P  -h3HzO  -  J  Her  +  r) 3Po+. although the phosphorous tribroniide is the first product it breaks up with water to form hydrogen bromide and phosphorus aoid. If sufficient water is not present, the phosphoiiium 10-bromide is formed and it will crystallize on the inside of the flask in beautiful yellow needle like crystals« Its formation is not to be desired as its explosive nature makes it dangerous» This reaction was oarried on in a large flask fitted with a two hole rubber stopper, a delivery tube and a small dropping funnel tube placed in the stopper. Th e end of the tube of the dropping funbefc WHS drawn to a fairly small point to break up the steam of bromine into small drops. The gas was purified by passing it through (1) a U tub e filled with water and a small quantity of red phosphorus. Thi s removed all traces of bromine that came from the generator as sometimes happened when the generating flask became hot. Th e gas was next passed through a wash bottle with more water and red phosphorus. The was^bottle was preferred to a seoond U  tub e for when a large quantity of gas -as coming through it bubbled the solution in the (J  tub e over into the next tube. The wash bottle was thus able to oatoh any of the solution. The U  tub e was prefered to another wash bottle because for the same length of solution through which the gas was made to pass there was less solution than in a corresponding length in a wash bottle,due to the greater diameter of the latter. The gas from the wash bottle was then conduoted through 11-two more long U  tube s containing phosphoric anhydride. Th e total length of drying material was then ahout sixty centimeters which was found quite sufficient. The diagrammatio view of this part of the apparatus is shown in figure 1 and includes the generator A, dropping funnel B , first (J  tub e for washing the gas 0, wash bottle D, and the two drying (J  tube s E and F. A  stop oook If enabled this part of the apparatus to be cut off from the rest of apparatus. THE APPARATUS FOR MEASURING VISCOSITY. Measurements described below may be considered under three headings: 1. Th e measurement of viscosity of the pure hydrogen bromide. £. Th e measurement of the viscosit y of solutions of acetic aoid in hydrogen bromide. 3. Th e measurement of the viscosity of solutions of ethyl alcohol in hydrogen bromide. The descriptions of the apparatus, mode of procedure and measurements will be discussed under these three heads* 1£ VISOOSITY OF PURE HYDROGEN BROMIDSo APPARATUS t For these measurements the apparatus was simple and is shown quite clearly in Figure I. The two legs of an Ostwald Tiscometer are lengthened by two tubes whioh project through a rubber stopper and are fitted with two (J  tube s to proteot the viscometer from outside moisture. Th e large tube has a side tube with a stop oock N  attache d to it. A Pentane thermometer 1  wit h a raage of +s~o'  to-* 00' graduated in degrees was used* I t was frequently compared to a pentane thermometer standardized by the Reichanstaldi. A small tube 0  wa s also put in the rubber stopper whioh was attaohed to a good water vacuum pump. Th e apparatus was enclosed in a large unsilvered Dewar flask G, in whioh was plaoed solid oarbon dioxide and ether for a cooling mixture. Usin g the suction mentioned above the carbon dioxide was made to boil at low pressures, and temperatures as low as-90° to-9 5 ° wer e ob ained without much difficulty. At all times the apparatus was kept perfectly dry. Th e faintest trao-e of moisture showing in the coloring of the hydrogen bfwnide. 13-MODE OF PROCEDURE: With She stop cook N opened and on allowing the Bromine from B to flow into flask A the hydrogen bromide was generated and caused to flow to the viscosity apparatus. Th e arer in the apparatus was allowed out through stop cook N attached to the larger ( J tub e and then olosed, thus forcing the gas through the tube H and I and out through U  tub e K. A s the apparatus was cooled below -68 °C th e gas condensed until sufficient was obtained to fill the viscometer tube to the mark used in calibrating it. Oare was taken to prevent the pressure rising t and as the gas sometimes condensed slowly a oonstant watch had to be kept as the liquid hydrogen bromide was forced out of the tube at K. In making measurements stop cook IT was closed. Ai r pressure was put on valve M until the liquid hydrogen bromide was forced up above the mark above bulb Z on the viscometer tube. Th e air pressure was then removed and the tube opened to the atmosphere and the time of flow taken. Oare was taken that the 0  tubes K and M were not causing a hindranoe to the flow of airt so tha t the pressure on the liquid in the viscometer tube would be at all times atmospheriOo The temperature could be varied within fairl y narrow limits by adjusting the vacuum and as the average of a uramber of readings was taken at each temperature, the results were accurate within observational error. -14-RBSULTS OF TBSTSt The results of three tests on pure hudrogen bromide follow in Table I« I n the first column is given the temperature in degrees centigrade below zero. I n the second is given the density of the hudrogen bromide calculated from figures given by D . Mcintosh and B.D. S-teELe (Phil . Trans . Royal , Soc. of London A, Vol. 205 Pg» 108) and in the third is given the time in mtnutes and in the fourth the relative viscosity for the *te»e tests. It was found possible to work baolc from known time and yisoosity of water to the constants 0 and &' for the tube and so to calculate the kinetic energy loss. Thi s was found to affect the results in only the fourth significant figure, therefore this oorreotion has not been used, as the experiment^/ error is greater than this. - 1 5 -VISCOSITY FO R HYDROGE N BROMIDE . TABLE I . Test A . Temp, -87 -86 -85 -84 -85 -82 -81 -80 -79,5 -78.5 -77.5 -76.5 -75.5 -74.5 -7S.5 -72,5 -71.5 -70.5 -69.5 -68.5 -67.5 -66.5 >ensjLtj__ 2.229 2.226 2.222 2.218 2.214 2.210 2.206 2.2025 2 .201 2.197 2.193 2.189 2.185 2.181 2.178 2.174 2.170 2.166 2.162 2,158 2.154 2.150 Time-Mins. .490 .480 .465 .460 .458 .452 .445 .439 .433 .427 .421 .417 .410 .405 .401 .402 .396 Viso .674 .658 .635 .621 .623 .616 .603 .594 .584 .574 .565 .559 .548 .540 .534 .534 .525 The curve s o f v i s cos i t y ani x temperatur e "bas e ar e shown i n G raph I . - 1 6 -l l l J B .U J I J I J - " • ' mi %ll-LI,..l,.|HMJ». DISCUSSION O F RESULTS . *J- ^ £ 1 ® ^ mjf.&eslM§<^ky(. ft tfrtm/J?, 4 3 / 0 7/  la  /J  /? M 7/ /f  /• -XT* The apparatu e fo r aeasvrln g tb e Tleeoelt y o f Mint leas e f Aoetl o Aoi d l a hydrege s brea d da ea e varied soacwba t fra a tba t l a Figur e 1 * A  aoeas wa s adopted fo r ooadsaala g tb e hrdroge s breald e apar t fra a tbe Tieooaete r tub e aa d tbe a lstrsduoln g I t lat e tb e tabe . Tbe apparatu e fo r tb i t procedur e i t show a l a Fig • t . Tb e hrdregsn breald e fa s paeee e lat e tb e large r graduate d tub a D threug^b/laaersed l a tb e ooolla g a lz ture . A  a—He r tub a leads fra a tb e hotte a o f tbi e tab e u p aa d l e jolae d tb e larger la g I o f tb e Tieooaete r tub e aea r tb e to p o f tb a apparatus, belo w tb e rubbe r stopper * Tb e tw o leg s o f tb e Tlssoaater tab e wer e le d ou t throug h tb e steppe r a s before * tbe saal le r ea e dlreo t t o a  dryin g tub e an d th e large r on e bad a  stoppe r l a th e to p aa d a  dryin g tub e attaobe d t o tb e s lds o f th i s a s shows . A  auotlo n tub s aa d a  pentaa e tberaoaete r were iaolude d l a th e apparatus , whic h wa e eaoloee d l a th e sea s Dewar flas k I . the sta p ees k 0  wa s opeals d aa d tb e ga s fra a th . hjaroge a broalde geaerate r bewea d A  was allowe d t o f l e e lat e tub e 9 where I t eoadeaoed . A  oosataa t aatebwa s aeeesaar y t o sa s tha t ! -18-none of the condensed liquid was pushed over into the visoometer tube. The acetic acid was introduced into the viscometer tube through H by means of the speoial pipette shown in Fig. 3. A s muoh acetic aoid as desired could be blown over by attaching a rubber tube to the end X  and inserting the long fine tube Y into the tube of the visoometer H L. The acetic aoid had to be blown over quickly before the tube became oooled and the aoid froze. B y weighing the pipette before and after, the weight of the aoetic aoid used was obtained. The hydrogen bromide was then blown over from tube D by applying air pressure at tube 0, stop cock B closed, until the bulb E was filled to the point to which it had been filled during calibration. The amount of hydrogen bromide used was calculated from the volume read off from the graduated tube D and the known temperature and density at that temperature. The density of the mixture was obtained by graduating the bulb E of the visoometer tube every millimeter and then finding the volume of the tube with water at 20" 6* B y noting the mark on this bulb at which the mixture stood at as wide a range of temperature as possible, a fairly olose determination of the density was obtained. During the first few trials, trouble was experienced in oondensing the hydrogen bromide without letting it run over into tube L. Thi s was easily done if the temperature was -19-kept below the freezing point of the hydrogen bromide. The gas liquified and then froze in the lower part of tube D, thus preventing the liquid from getting into tube L before it was required there. In making measurements, air pressure was applied at tube S (stop oooks C & B were closed) thus forcing the liquid up to bulb M. TThe n the level of the liquid rose above the upper mark the pressure was removed and the tube S opened to the atmosphere* RESULTS OF TESTSt The observations and oaloulations of this series of tests are set forth in the following table. The oaloulations were made as stated in the "Mode of Procedore". The Kinetic energy correction was left out forthe reason that it was not necessary in view of the magnitude of the observational error. In the tables the first column gives the temperature in degrees below zero; the seoond oolumn gives the time In minutes; the t^ ird, the density of the mixture; the fourth, the visoosity in oentipoiseSo Th e other data is given at the bottom of eaoh table* - 2 0 -VISCOSITIES O F AOBT I IN HYDROGE N TABLE Tenrp. Tim e 8 4 . 1 8 2 . 1 8 1 . 6 8 1 . 1 8 0 . 1 7 9 . 5 7 9 . 0 7 6 . 5 7 5 . 5 7 4 . 3 7 2 . 6 7 0 . 5 6 9 . 5 6 7 . 0 2 . 4 5 4 2 . 2 3 5 2 .209 2 . 1 6 7 2 .107 2 . 1 0 5 1.998 1.902 1 .875 1.796 1 .696 1 .618 1 .548 1 .508 Weight o f A o e t i o Weight o f Hydrog i °/o o f A o e t i o Ao i d i AOI D SOLUTION S BROMIDE. I I . Density Visoosity . 1.972 1.960 1.958 1.956 1.950 1.948 1.945 1.935 1.928 1.922 1.913 1.903 1.895 1.885 3 .04 2 .75 2 .71 2.66 2.57 2 .55 2 .44 2 .31 2.27 2.16 2.03 1.93 1.84 1.78 id B  .838 9 gms. Bromide "  8.681 9 gms - 8.65 $ - 2 1 -TEST 0. Temp. 84.6 82.1 81.6 80.6 79,4 77.5 Weight Weight Time 1.167 1.112 1.085 1.125 1.133 1.042 of Acetic Acid of Hydrogen fo of Acetic Acid Density 2.167 2.148 2.143 2.134 2.123 2.105 8 Bromide " = Visoosityo 1.59 1.50 1.46 1.51 1.51 1.38 •4252 gms. 10.691 gms . 3.885 j6 Test D . Temp. 82.5 81.9 81 80.3 79.3 77.5 75.3 73 Weight Weight Time .932 .913 .902 .891 .856 .83 .820 .807 of Aoetio Acid of Hydrogen io o f Acetic Acid Density 2.155 2.149 2.141 2.134 2.114 2.108 2.087 2.065 s Bromide = Viscosity. 1.26 1.23 1.21 1.19 1.14 1.10 1.07 1.05 .4234 gms 10.69 gms. 3.80 % - 2 8 -TEST 3 . Temp. 84 .5 82 .5 75 .1 71.1 66.0 65 .0 Weight Weight of of Time 5.79 4 .92 3.818 3.578 3.114 3.089 Aoetio A G Hydrogen $ o f Aoet i c Aoi d i d Dens i ty 1.858 1.840 1.778 10744 1.702 1.694 Bromide S • • V i s c o s i t y . 6.96 5.65 4 .26 3.92 3.39 3.28 1.1257 gms . 8.725 gms . 11.49°/ TEST F . Temp. 84 .5 81 .5 79.0 78.0 77.0 75 .5 75.0 74 .5 71.5 71.0 Weight Height of of Time Dens i t y .750 2.17 5 .710 2.17 2 .688 2.16 6 .681 2.15 8 .641 2.15 5 .635 2.15 2 .628 2.14 8 .620 2.14 6 .620 2.13 6 .617 2 .13 4 Aoetio Aoi d = Hy&rogan Bromid e = fo o f Aoeti o Aci d s V i s c o s i t y . .999 .965 .932 .921 .866 .856 .846 .834 .831 .826 .4780 gm s 12.99 gm s 3.38 fo - 2 3 -u *V 6X  4f  /*  7/  rz  73 P^y/T^s Cerf/7qrcxde  i ^ n - Z c r i would b e g r e a t e r . - 2 4 -I t ha s bee n foun d t h a t th e v i s c o s i t y o f a c e t i o a c i d i n hydroge n bromid e r i s e s abov e t h a t o f hydroge n bromld * and i n t h e mor e concen t r a t e d s o l u t i o n s o f a c e t i c a c i d , th « V i s c o s i t y r i s e s abou t t h a t o f a c e t i c a c i d a t 85degre# s c e n t i g r a d e . Thi s woul d p o i n t t o t h e fac t t n a t bo t h l i q u i d s wer e a s s o c i a t e d an d t h e mixin g o f the m cause d a m a t e r i a l decreao e o f d i s s o c i a t i o n . Within 12i e l i m i t s o f th e r e s u l t s i t ca n b e see n t h a t t h e i n c r e a s e o f th e pe r cen t o f a c e t i c a c i d i n c r e a s e s the v i s c o s i t y (  i . e . lower s th e a s s o c i a t i o n ) an d i t a l s o makes th e chang e o f V i s c o s i t y pe r degre e g r e a t e r whic h ma y be see n fro m th e s l ope s o f th e curves . VISCOSITY Q g ETHY L ALCOHO L O f HYDROGE N BROMIDE APPARATUS This appa ra tu s show n i n f igur e A  wa s designe d t o e b v i a t e som e o f th e appa ren t i n a c c u r a c i e s o f th e appara tu s shown i n f i g u r e Tw o an d a l s o t o spee d u p th e t r i a l s . The tub e A  goe s r i g h t t o th e botto m o f th e l a r g e r g radua ted tun e C . Th e to p o f tub e C  narrow s wher e i t goes throug h th e rubbe r s toppe r an d a  T  p iec e connect s i t whic h a  dryin g tub e D  f i t t e d witf e a  s t o p coc k E . A s a a l l e r tub e l e ad s fro m th e botto m o f Tub e C  t o th e l a r g -er l e g L  o f th e Viscomete r t u b e . Th e tw o l e g s o f th e viscometer tub e wer e extende d throug h th e cor k an d wer e a t t a c h e d t o dryin g tube s e n th e sam e was ; a s i n f igur e 2 . At th e botto m o f th e viscomete r a  smal l tub e Q was a t t a c h e d whic h wa s turne d u p an d jo ine d t o a  c a p i l l a r y -25-tube 1 which was graduated in millimeters. This tube was attached to tube H of about 1,5 co capacity and a small tube from this larger wne lee(d to a n absorption bottle P. The usual pentane thermometer and suction tube were included • The whole apparatus is place d in the Dewa r flask K as before. MODS OW  PROCEEElffiE: The hydrogen bromide gas enters through A and is led to the bottom of tube 0. Her e it is cooled and con-ienses . A s soon as sufficient liquid condenses to cover the bottom o f the tube the stop cock E is opened and the rest of the gas bubbles up through the condensate and quickly condenses. I t was found that, by keeping the temperature at about -87 degrees, after a cubic centimeter or so condensed, the gas could be forced in as fact as it could be j&operly d*i«& in tubes E and B1 figure 1. This was a very much more rapid way of condensing the gas ana. there was not the danger of the liquid going into the tube L, I f the flow wa s kept within reasonable bounds. The ethyl alcohol was introduced into bulb J by means by the pipette used before and the weight used as-certained in the same way. Th e hydrogen bromide was blown over by closing stop cock B and applying air pressure at tube Bt when reading the graduations on Tube 0 both tubes E and A were open to the atmosphere so thatthe level of the 26 . l i q u i d wa s th e sam e i n bot h inne r an d oute r tubes . The weigh t o f hydroge n bromid e use d wa s obtained fro m th e volum e a s rea d ,  th e know n temperatur e and densit y f o r tha t temperature . I n makin g th e measure -ments th e so lu t io n wa s r a i s e d t o th e mar k abov e bul b B b y applyin g a  gentl e suct io n a t tub e Y  ins tea d o f applying a i r pressur e t o tub e W . To determin e th e densit y th e so lu t io n wa s sucke d u p to f i l l bul b R . Th e so lu t io n remainin g i n bul b J  wa s removed b y th e ai d o f a  lon g tub e an d a  suctio n pump . The l iqu i d i n R  wa s the n allowe d t o flo w dow n an d bul k H. wa s sucke d ful l t o ma^ k e U  jus t abov e i t c Th e colum n of l iqu i d wa s the n broke n b y blowin g th e r e s t o f th e l i qu id i n th e viscomete r throug h tub e V  past th e entranc e to tub e G  and wa s l a t e r remove d b y suctio n b y wa y o f Tube V 0 This l e f t th e tub e H  f i l l e d t o mar k U  o n on e sid e and t o som e plao e i n th e graduation s o n tub e £* • Th e chang e in volum e o f th i s l iqui d wit h temperatur e wa s j»ote d b y th e graduations o n tub e F . Th e l iqu i d i n H  was slowl y boile d off an d th e ga s caugh t i n absorptio n b o t t l e P . Th e ethy l alcohol wa s vaporize d b y surroundin g th e bul k H  wit h wate r and slowl y heatin g i t . The b o t t l e P  wa s weighe d befor e an d af te r absorptio n and th e weigh t o f th e solutio n whos e volum e chang e wa s ffoted wa s i n th i s wa y found . Th e densit y wa s the n c a l -culate do -27-KBSTILTS OF TESTS. The observations and calculations of this series of tests are set forth in the following table. Th e calculations of density were made as explained above. The Kenetio Energ y oorreotion was omitted for the reason stated previously* In the tables are given, first the temperature in degrees centigrade below zero, second the time in minutes, third the density of the mixture and fourth the viscosity in oentipoises. The remaining data are given at the foot of each tableo TEMP. 86.5 86 85 84.5 81.5 78.5 77 76.5 76 75.5 Weight Weight % Ethyl of of TABLE TIME. .618 .614 .601 .597 .568 .550 .535 .525 .517 .510 Ethyl a III. DENSITY 2.163 2.158 2.148 2.143 2.113 2.083 2.073 2o063 2.058 2.054 lcohol Hydrogen Bromide aloohol VISCOSITY. .965 .956 .932 .923 .866 .853 .800 .781 .768 .756 • .350 5 gms. • 5.429 2 gms. 6.06$ 2 8 . T ^ T H . TKMPSRATUBB 0 6 . 5 8 5 . 6 8 4 . 5 83 82 BUS 8 0 . 7 8 0 . 5 80 7 9 . 6 7 8 . 7 7 8 . 5 7 6 . 6 7 4 . 6 7 2 . 6 7 0 . 6 6 9 . 5 6 6 . 6 TIMB . 6 6 0 . 5 5 3 . 5 4 0 . 527 . 6 2 0 .517 . 6 1 4 . 6 1 1 ,507 . 6 0 4 . 5 0 3 . 6 0 0 . 4 8 4 . 4 7 4 . 4 6 6 . 4 5 3 . 4 4 8 . 4 4 0 DENSITY 2 . 2 0 2 . ^ 9 6 2 . 1 8 9 2 . 1 8 1 2 . 1 7 6 2 . 1 7 1 2 . 1 6 8 2 . 1 6 7 2 . 1 6 4 2 . 1 6 1 2 . 1 5 8 2 . 1 5 6 2 . 1 4 3 2 . 1 3 1 2 .119 2 .107 2 . 1 0 1 2 . 0 9 3 VISCOSITY . 8 8 9 . 8 7 6 . 8 5 3 . 8 2 9 . 8 1 6 1 . 8 1 0 . 8 0 4 . 8 0 0 . 7 9 2 . 7 9 6 . 7 8 8 . 777 . 7 4 9 . 7 2 9 . 7 1 1 . 6 8 9 . 6 7 9 . 6 6 6 Weight o f S t h y l a looho l .260 4 gms . Weight o f Hydroge n Bromid e 11.7 4 g»s . % o f S thy l Alchho l •  2 .09 $ 29. TEST I TEMPERATURE 87.5 85 85 81*5 79.5 77.5 74.5 71 70 69.5 68.5 TIME .479 .466 .457 .450 .440 .431 .4168 .403 .402 .398 .390 DENSITY E.186 2.174 2.158 2.146 2.130 2.114 2.090 2.062 2.054 2.042 2.034 VISCOSITY .754 .731 .712 .697 .682 .657 .629 .599 .596 .587 .572 Weight of Ethyl Alcohol .430 0 gms. Weight of Hydrogen Bromide ll o50 gms< $ of Ethyl Aloohol 3.6 $ 30. TEMPERATURE 87 86 85.5 84 82.5 81.5 80 78.1 76 73.5 73 69 TEST J. TIMS .473 • 464 .460 .448 .437 .430 .421 .414 .408 .401 .397 .391 DENSITY 2.213 2.208 2.205 2.198 2.191 2.186 2.179 2.169 2.159 2.146 2.139 2.124 VISO .775 .741 .732 .711 .691 .678 .662 .647 .636 .621 .599 .555 Weight o f E thy l Alcoho l .165 3 gms . Weight o f Hydroge n Bromid e 11.85 7 gm s % o f E thy l Alcoho l 1.38 9 3 1 . TEMPERATURE 86 85 83.5 88 80.3 79.5 78 76.5 75 72.6 70.6 69 68.7 TEST X. TIME .470 .458 .445 .434 .423 .418 .410 .402 .396 .387 .381 .377 .376 DENSITY 2.217 2.213 2.207 2.200 2.194 2.190 2.184 2.178 2.172 2.162 2.154 2,148 2.146 VISCOSITY .752 .731 .709 .689 .669 .661 .646 .632 .621 .604 .592 .584 .582 Weight o f E thy l Alcoho l .059 6 gms . Weight o f Hydroge n Bromid e 9.781 1 gms . % o f E thy l Alcoho l .60 6 # 67 / * / / 7Z -33 CONCLUSION. The result s sho w that association o f th e Ethyl aloohol and acetic acid are affected "b y the liqui d hydrogen bromide. Th e aoetic aci d i s affected t o a greater exten t du e no doub t to it s stronge r aoid characteristics . The ethyl alcohol ha s a high equivalent conductanc e about thre e times th e value o f the equivalen t conductanc e of aoetio acid . C.A. Krau s (Propertie s o f Electrically Conductin g Systems; Chemical Catalogu e Co . Ne w York 1922, Chap. 5) proves tha t ther e i s a definit e relatio n between th e viscosity of a substance and it s conductiTity . The viscosity varies inversel y as the conductivity . This would sho w that ethy l aloohol would have a lowe r viscosity tha n aoetic aoi d and s o would have th e lowe r visoosity i n the hydroge n bromide. STO.If.IA.EY. Measurements o f viscosity o f iur e hydrogen bromid e have been made an d compared t o those o f previous investigators . Measurements o f visoosity o f certain concentrations o f solutions o f aoetic aoi d and ethyl aloohol i n hydrogen hav e been madeo The effec t o n the visoosity o f hydrogen bromide o f the addition o f these liquid s has been noted an d i t has been show n tha t the result s were i n aocordance with th e -34-work of other investigators on associated liquids. In conclusion I wish to thank Dr. Archibald for his kindly assitance at all times and Dr. M.J. Marshall for assistance in making some of the apparatus• 


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