Conductivities and viscosities in pure and in mixed solvents; radiometric measurements of the ionization constants of indicators, etc

Harry Clary Jones

Sujets

• Viscosity
• Electrolyte
• Conductivity

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• Publié par: les_archives_du_savoir
• Nombre de lectures: 6
• Langue: English
• Poids de l'ouvrage: 11 Mo

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UNIVOF
TORONTO
LIBRARYANDCONDUCTIVITIES VISCOSITIES IN PUKE AND
MIXEDIN SOLVENTS
MEASUREMENTS OF THERADIOMETRIC
CONSTANTSIONIZATION OF
ETC.INDICATORS,
BY
C. ANDHARRY JONES COLLABORATORS
D. C.WASHINGTON,
BY THE CARNEGIE INSTITUTION OF WASHINGTONPUBLISHED
1915CARNEGIE INSTITUTION OF WASHINGTON
PUBLICATION No. 230
PRESS OF GIBSON BROTHERS
D. C.WASHINGTON,rrr
PREFACE.
The discussed in this at firstinvestigations monograph might seem,
to dealwitha of some ofwhichhave nosight, variety subjects, closevery
relation to the but all of these lines of work wereothers; nearly sug-
the solvate of solution as here aboutgested by theory fifteenproposed
and have been carried out with the ofyears ago, specific purpose
their on thisascertaining bearing theory.
Dr. Davis studied the viscosities of solutions of caesium salts in mixed
in ofand mixtures the associated formicsolvents, liquids water, acid,
and acetic in its relation to the ofacid, theory viscosity proposed by
Jones several years ago.
Dr. Davis and Dr. Putnam the ofinvestigated dissociating power
formamid as a in connection with its on a of thesolvent, bearing theory
relation between the of a solvent and otherdissociating power physical
of that its dielectric constant and its ownproperties liquid; namely,
association.
Dr. Shaeffer and Dr. Paulus used the new constructedspectroscope
"
to the nature of solvent to determine the constants ofstudy bands,"
indicators a essential to the scientific use of thesequantity absolutely
substances in quantitative analysis.
This work was extended Dr. Paulus and Mr. Hutchinson to theby
corallin.indicator,
found suchamarked differencebetween the behaviorHaving physical
towards of free and of combined Dr. J. E. L. Holmes tooklight water,
the of a reaction effected the ions of water theup study by saponifica-
tion of an ester to see whether difference in the chemicalany activity
of free and of combined water could be detected. It seems that such
a difference combined water chemicalexists, having apparently greater
than free water.activity
This work was extended Mr. to another reaction whichby Connolly
much more the of aceticproceeds rapidly hydration anhydride.
This work has not been extended to finalyet sufficiently justify any
conclusion.
The work two on the conductivities of acidsbegun years ago organic
in was extended Dr. and Mr.ethyl alcohol, greatly by Lloyd Wiesel,
the of of the more common acidscomprising study nearly forty organic
in this solvent. The aim of thiswork is to arrive at a of theknowledge
dissociation of these substances and the of solvationby alcohol, degree
of these in alcohol.compounds
aDr. Watkins has extended work in this aboutlaboratorybegun
water.dozen on the and dissociation of salts byyears ago conductivity
and has obtainedHe has studied a number of the less common salts,
the conclusions drawnaccurate results in confirmvery which, general,
from our earlier work in this field.
iniv Preface.
of combinedThe different behavior of free and waterphysical
of the relative disso-to Dr. Shaeffer the desirability studyingsuggested
water. This work was under-of free and of combinedciating powers
He isochloric solutions of thetaken Mr. Ordeman. preparedby
salt and of thehydrated potassium chloride, strongly hydratedslightly
and used these solutions as solvents in which tosalt calcium chloride,
dissolve chlorides and measure their dissociations. The dissociation
of a number of salts in these solvents was measured and while we are
;
not to draw final it seems thatyet prepared any conclusions, probable
"combined" water has rather less than "free"dissociating power
water.
The and of the saltabsorption adsorption slightly hydrated potas-
sium is of both scientific andchloride a technicalby soils, problem
Work has been in in on thisimportance. progress my laboratory
the Mr. with the ofproblem during past year by McCall, cooperation
Messrs. F. S. and Trelease. findHildebrandt, Johnston, Holmes, They
that a of the chloride is absorbed or combined chem-part potassium
with the soil and a is adsorbed or in a state ofically particles, part
union with the of the soil. Under certain conditionsphysical particles
the solvent be more adsorbed than the salt.may rapidly
The results of these of which have been carriedinvestigations, many
out with the aid of awarded me thegrants generously by Carnegie
Institution of are all recorded in thisWashington, publication.
HARRY C. JONES.
JOHNS HOPKINS UNIVERSITY,
1915.June,CONTENTS.
I. CHAPTER IICHAPTER Continued.
PAGE PAGE
THE VISCOSITIES OF SOLUTIONS OF CAESIUM Caesium Nitrate in Formamid 32
SALTS INMIXED THEVISCOS- Lithium in 33SOLVENTS;
ITIES OF BINARY MIXTURES OF THE Barium Chloride in 33
ASSOCIATED FORMIC Mercuric in Formamid 34LIQUIDS, WATER,
Acn> AND ACETIC TOGETHERWITH Cobalt Bromide in 34ACID,
SOME NEW FORMS OF APPARATUS. Sodium Chromate 37
Mercuric Chloride 38
Introduction 3
Cobalt Bromide 38
Historical 3 Csesium Nitrate and Chloride 38
and Procedure 6Apparatus or Results 39Summary
Discussion of Results 8
The Viscosities of Mixtures of theBinary
CHAPTER III.Associated FormicLiquids, Water,
Acid and Acetic Acid 10
RADIOMETRIC MEASUREMENTS OF THE IONI-
Some new Forms of Apparatus: ZATION CONSTANTS OF INDICATORS I.
a Substitute for the Twin-Bulb inI, Trap
of the 41
. ... 13 Purpose InvestigationToluol-Mercury Thermo-regulators
Historical 42a new Form of for 14II, Pyknometer Liquids
The Radiomicrometer 44
The 48SpectroscopeCHAPTER II.
Source of 50Light
TheTHE CONDUCTIVITYAND VISCOSITY OF SOLU- Cells 50
ofTIONS OF CERTAIN SALTS IN FORMAMID 51Arrangement Apparatus
DifferentialAS A SOLVENT. The Method 52
Theoretical Discussion 52
Previous Work in Formamid 17
Work on 57Experimental Methyl OrangeFormamid as a Solvent 18
Results with 59Methyl Orange
Purification of the Solvent 20
64Phenolphthalein
Salts 23
Results with 66Phenolphthalein
Solutions 23
72Summary
24Conductivity Apparatus
24Viscosity
Thermostats 24 CHAPTER IV.
Discussion of Results 24
RADIOMETRIC MEASUREMENTS OF THE IONI-
of the Various Solvents 24Comparison
ZATION CONSTANTS OF INDICATORS II.Sodium Bromide in Formamid 25 Iodide in Theoretical Discussion 73 25
Sodium Chromate in Work on Rosolic Acid 75 26 Preliminary
Potassium Chloride in Results with Rosolic AcidFormamid 26 79 Iodide in Rosolic Acid as a Dibasic Acid 80 27 in Formamid .... 27 82Sulphocyanate Summary
Ammonium Bromide in Formamid 28 Iodide in 28 CHAPTER V.
Chloride in Forma-Tetramethylammonium
THE ACTION OF SALTS WITH WATER OFmid 29
HYDRATION AND WITHOUT OFIodide inFormamid. . 29Tetraethylammonium ON THE VELOCITIES OPRubidium Chloride in Formamid 30
SAPONIFICATION OF ESTERS. Bromide in 30 Iodide in Formamid 31 Reaction Chosen 85
Rubidium Nitrate in 31 Historical 86
Caesium Chloride in . . 32 Hydrolysis 88Content*.VI
VII Continued.CHAPTERV Continued.CHAPTER
I'AOB
PAGE
Benzoic Acid
of ProblemStatement
Acidw-Chlorbenzoic
Apparatus Acid?/i-Nitrobenzoic
Solutions
AcidDinitrobenzoic
The Esters
137Picric Acid
IndicatorThe Base and
AcidSulphosalicylicof ProcedureMethod
Acido-Aminobenzoic
Calculations
Acidp-Aminobenzoic
Data
Acido-Toluic
Discussion of Results
Acid7>-ToluicSummary
138AcidCinnamic
Phthalic Acid
VI. AcidCHAPTER Dichlorphthalic
Anisic Acid
ON THEOF NEUTRAL SALTSTHE EFFECT 138Mandelic Acid
ANHYDRIDE.OF ACETICHYDRATION
AcidCamphoric
Results 139of Acetic Discussion of theAnhydrideHydration
and Conduc-Salt Action Relation betweenNeutral Composition
Problem 142of theStatement tivity
115MaterialsPurification of ;
SolutionsandApparatus
CHAPTER VIII.
Manipulation
Discussion TEMPERATURE COEFFI-CONDUCTIVITY,
118Conclusion AND PER-CIENTS OF CONDUCTIVITY,
DISSOCIATIONS OF SOMECENTAGE
UNUSUAL SALTS INRATHER AQUEOUS
CHAPTER VII.
SOLUTIONS.
OF CERTAIN ORGANIC ACIDSCONDUCTIVITY
147Apparatus
IN ETHYL ALCOHOL.
and Rheostat 147Bridge
119 Cells 147SketchHistorical
129 Constant of Baths 147Work Temj>eratureExperimental
129 Vessels 147ContainingReagents
130 Solutions 147
Apparatus
131 Water 147Procedure
133 Salts 148Results
148Acid 134 StandardizationPhenylacetic
Acid 134 Cell Constants 148Oxyisobutyric
Acid 134 Precautions 148Brompalmitic
134 Results 149Malonic Acid
Acid 134 Sodium Bromate 150Ethylmaloni*
Acid 134 150SulphocyanateDiethylmalonic
Acid 134 Sodium 150ThiosulphatePropylmalonic
Acid 135 Dithionate 151Dipropylmalonic
SodiumAcid 135 151Butylmalonic Pyrophosphate
Acid 135 Trisodium 151Allylmalonic Phosphate
Acid 135 Sodium 153Benzylmalonic Dihydrogen Phosphate
Monobromsuccinic Acid 135 Tungstate 163
Dibromsuccinic Acid 135 Sodium Formate 153
Sebasic Acid 135 Chromate 154
Acid 135 Sodium DichromateThiodiglycolic 154
Benzilic Acid 135 Potassium 154Ferricyanide
Maleic Acid 136 Ammonium lodate 155
Fumaric Acid 136 156Dihydrogen Phosphate
Itaconic Acid 136 Chromate 156
AcidMesaconic 136 Ammonium 157Sulphocyanate
Acid 136 Lithium ChromatePhenylpropiolic 157
Aconitic Acid . . . 136 Rubidium I