tts ©f T M T I A H X - m m H3CP0CHL0RITS FOR OXIDATIONS Clayton Bdward fan Ball A f88®IN Submitted to the School of Advanced Graduate Studies of Mchigan State University of Agriculture and Applied Science in partial fulfillment of the requirements for the degree of D o o m OF FHliOSOFHI Department of Ghsaulstry 1956 ProQuest Number: 10008515 All rights reserved INFORMATION TO ALL USERS The quality of this reproduction is dependent upon the quality of the copy submitted. In the unlikely event that the author did not send a complete manuscript and there are missing pages, these will be noted. Also, if material had to be removed, a note will indicate the deletion. uest. ProQuest 10008515 Published by ProQuest LLC (2016). Copyright of the Dissertation is held by the Author. All rights reserved. This w ork is protected against unauthorized copying under Title 17, United States Code Microform Edition © ProQuest LLC. ProQuest LLC. 789 East Eisenhower Parkway P.O. Box 1346 Ann Arbor, Ml 4 8 1 0 6 - 1346 AGKHOW^EDGfMf The author wishes to express hi® sincere appreciation to Ur, Kenneth Q, Stone for his most helpful counsel and guidance during the course of this work. ii VITA Ham©; Clayton Edward Van Hall Born* April 2k9 192k in Grand Rapids, Michigan Academic Garears Grand Haven High School, Grand Haven, Michigan (1938-19U2) Hope College, Holland, Michigan (19U6-19U9) Michigan State University, East Lansing, Michigan (1952-1956) Degrees Helds A* B« Hop© College (19U9) M. S* Michigan State University (195U) iii m «ss m nrnxtmmm. for wow-Aararms G rro*vroiia ^w.ww||i|,4»lV3wp sMwara v # w B * j$? ISEBIOT state W i S W i S ^ ' #$*' A®8SpStw# ft*¥^ |@ieief in -^R ai ^f ■j he ll uf c'^l-'WBkjASilvflSi* wSr w Aii ,l '« r i^^MbuiaM^afli^StitiitoHfeMMi^aMilk^ltiijfliL jpvei4uiiyW J UJ £P1 3'M M’ji3b■ * ♦ ft l> jf r fer the degree #f w m o r «r f w & m m m SspsirtiiBiisS #C Oh^Ksiistry mmm fhe OS* of boon in s tig a te d SQjTfcOSOO Ofc'QOI o o - s s is jr s s s ' ak eew^ for B^HHtaoous ossldetiOiMi bm rnmm& im the iM s im t e o f a U a ite d - MfciHiejMtfSSMlW'Afc' O f’OF jEK^SSAiS^* s^s^sssoSpteOOSAoOIS' Seliitlssis of tootm*^|tr^i!fL uso set iwhnN^IH* setiig i^poehljOjsSte- oetot to yt1iffiew** o r s i e sooroe o f ehtostoe* metoH*e sst* stiidtoii £& efWftteeotee of th st s&hii the eeshto tfrflftffi skth eseerol pft.eee the res@ttsss SSJ?* to© OlOS SiSd SO. OSOeSS Of rOOS^^t OSS OOtSSIASd# ifces&tieKt rote Sttidles la ajl.afcttijtl gfc&stto iweftA HSlaw an SXSiOO Of the llVVieSttlSStte S9Xl lltbtoe ehtorto# on & oserse of j^leiftos ostihldS'hed 'that the oddities of ehloiijie ooo reijid hot that so oateess &t sklertos iso osenssod# fhe direot ti.to stiw of oissotiiirstss sftto tsrt*toiy3L i^rj^ehlorite Tus&it»et tffisibla <£***» tn the sloe reeettos rate* OSIjbo the Ja&KJOehtorite .Si m m m m of oKlo3Piao f t mm pm&l&M to titrat® ojioatorotoe ssp^o* m fotstyMOt»^oOI3r to .#ootoi «ootto seid* With the o f otim so o il ossitsrotoo teotod yioldod M .#i s?#oult» ouhstll^tloxi or lo v C#3p®nixfLis©#sa iaffftt.'f.ii%$* ii&ar&tuid 4® i*y adLtih, i^jKW jhM rito atata a r a» a mww& ®f $&m$m Uut M # s M l& l mm obtained im fe©*& t t i mMmm* smild »a* fea datamiaad, 4tiMMri£$r or i*aii3*aaii|r hmm»® tim mmUm wm too alow* nd TABLE OF CONTENTS Page INTRODUCTION.*....... ..................................... II HISTORICAL..... .,*,.... ....................... .......... 3 . I A, The Properties of Alkyl hypochlorites,................ B. The Preparation of Alkyl Hypochlorites................ G, The Reactions of Alkyl Hypochlorites.................. III EXPERIMENTAL *..... ............................... 3 k 5 8 A* Apparatus,..... ........ 8 B. Reagents and S o l u t i o n s , ........... 9 C. The Standardisation of tert-Butyl hypochlorite Solutions. ............... ........... 11 1* Iodine-thiosulfate Method ...... ............... 11 2, Excess Oxalate Method,............................. lU a. Selection of Standard,........ lit b. Reaction Rate of tert-Butyl Hypochlorite with Excess Sodium Oxalate .... 15 c. Determination of Sodium Oxalate with Geric Sulfate,« 1 8 19 d. Standardisation Procedure* ..... D. The Stability of tert-Butyl Hypochlorite......... 21 1, Effect of Water, .... 21 23 2* Effect of Reducing Substances................ 3. Acid-base Catalysed Decomposition. .............. 27 lu Light Sensitivity,.;,,,,,,,*,.,..*.,.*.... 29 E* Endpoint Detection,................................... 30 1, P o t e n t ! o m e t r i c 31 2. A m p e r o m e t r i c 32 F. tert-Butyl Hypochlorite as a Source of Chlorine....... 33 G. Determination of Unsaturation. ..... 35 1. Excess Hypochlorite M e t h o d . 36 2, Excess Chlorine Method .... 39 3* Direct Titration with tert-ButylHypochlorite as a Source of C h l o r i n e i j . 2 a. Potentiometric Titration of Styrene............. hZ b . Amperometric Titration of S t y r e n e ......... U5 c. Amperometric Titration of Other Unsaturates..... U6 d. Effect of Temperature ..... U8 e. Effect of Mercuric C h l o r i d e . . . . . . . 50 vii 1 TABLE OF CONTENTS - Continued Page H, Miscellaneous Oxidations.............................. 1. Sodium Oxalate..................................... 2. Benssaldehyde......... 3. Phenol...... ..... U, Hydroquinone. .... * IF 67 SUMMARY. .... LITERATURE CITED... APPENDIX 53 53 57 58 62 69 ..... ..... 72 viii LIST OF TABLES TABLE I H HI I? V VI VH VIII Page Effect of Air Oxidation and Reaction Time on the Standardisation P r o c e d u r e 13 Reaction Rate of tert-Butyl Hypochlorite -with Excess Sodium O x a l a t e . 17 Determination of Sodium Oxalate with CarloSulfate........ 19 Standard!zation of Ilypochloriie Solution by Excess Oxalate Method. .... 20 Standardisation of Hypochlorite Solution by Iodine-* Thioeulfat© M e t h o d 21 Acid-Base CatalyzedDecomposition................ 28 Light Sensitivity of tert-Butyl Hypochlorite in Glacial Acetic A c i d 30 Potentiometric Titration Results of S t y r e n e kk 12 Amperometric Titration Results of Styrene................. k$ X Amperometric Titration Results of Several Unsaturates..... 47 XI XH XIII XI? X? XVI XVII XVIII Effect of Teipsraiur© on Titration Results. Effect of Mercuric Chloride on Titration Results Comparison of Titration Results 4 9 .... ..... Reaction Rate of Sodium Oxalate with Excess tert-Butyl Hypochlorite .... Decomposition of Chlorine in Eighty Per Cent AceticAcid.. $1 53 54 $6 Determination of Sodium Oxalate with Excess tert-Butyl H y p o c h l o r i t e 57 Oxidation of Benaaldehyde 58 ..... Amperometric Titration Results of Phenol........... ..... ix 61 LIST OF FIGURES FIGURE I II HI IV Page Effect of Water on the Stability of Acetic Acid Solutions of tert-Butyl hypochlorite*.*..**...**.** 2k Effect of Reducing Substances on the Stability of Acetic Acid Solutions of tert-Butyl Hypochlorite. 2 6 Galvanometer Beflection with Various Chloride Concentrations 3U in Glacial Acetic Acid........... Reaction Rates of Several Unsaturates with tert-Butyl hypochlorite* *.... 33 V Reaction Rates of Several Unsaturates with Chlorine*.....*.. i*X VI Potentiomotric Titration of Styrene with tert-Butyl I^pochlorite as a Source of Chlorine.................**....* U3 Amperometric Titration of Phenol with tert-Butyl ........ hypochlorite. 60 Amperometric Titration of Hydroquinone with tert-Butyl hypochlorite as a Source of Chlorine........................ 63 Amperometric Titration of %droquinon© with tert-Butyl hypochlorite 6$ VH VHI IX x 1 I mmomGnzm Jlthmigh mn*mqP'Qm& solvente have received m e h attention in their application* to acid-base titrations, little work has been reported on the as© of non^aqueous selveaie as media for direst volumetric determin­ ations with oxidising and reducing agents, this is due primarily to the lack Of reagents that can be used in non-aqueous solvents. Previous reported work concerns the use of inorganic oxidizing and reducing agents, fomecek and Heyswsky (37) investigated the us© of a uuuaber of such oxidants in glacial acetic acid., these were bromine, chromic acid, and sodium permanganate, fomeeek and Valeha (38) extended this work to include the use of iodine, iodine monoehloride, Iodine monobroraide, and lead teifca&cetat©* Hinsvark (20) has meed glacial acetic acid solutions of eerie nitrate for the determination of simple oxygenated organic compounds» the number of reducing agents that have been used in non-aqueous solvents is fewer* IHnsvark and Stone (21) have recommended ferrous perchlorate in facial acetic acid as a reducing agent* Hovotny (26) has reported the use of vanadyl acetate in glacial acetic acid and Freedman (12) has investigated the use of sulfur dioxide in pyridine for the determination of organic compounds containing positive halogens* Tomecek and Heyrovsky (37) have also reported the us© of glacial acetic acid solutions of titanous chloride. Most of the inorganic reagents investigated thus far have two disadvantages. Solutions of the reagents in non-aqueous solvents are 2 unstable and their lew solubilities limit the concentrations obtain­ able* Another prominent reason for the slew progress in this field Is the excessive east and disagreeable properties of the solvents them­ selves . An organic oxidizing agent which map prove adaptable for use in volumetric analytical determinations in non-aqueous solvents is iert* butyl hypochlorite, organic chemistry. This compound has found some use in preparative Many of Its reactions are characterised by high yiOlds obtained rapidly with moderate conditions* The purpose of this work m s to investigate the use of tert-buiyl hypochlorite as an oxidizing agent for analytical determinations of organic compounds in non-aqueous solvents. Glacial acetic acid m a used as the solvent because of its high purity, stability, and moderate cost* 3 IX HISTORICAL A. The Properties of Alkyl Hypochlorites The alkyl hypochlorites are organic esters* They are pale yellow liquids, immiscible with water, with very irritating odors similar to chlorine* The primary and secondary alkyl hypochlorite© are very unstable and decompose explosively when exposed to bright light* Even in darkness they decompose rapidly liberating sufficient heat to cause boiling* The tertiary alkyl hypochlorites are very stable, tert-Butyl hypochlorite can be distilled without change and kept for months with very little decomposition provided light is excluded. B.P. « 79.6°C/ is 750 ram., d4 * 0.9563 (6}« tert-Amyl hypochlorite does decompose on distillation, but it may be kept at room temperature with little change, When exposed to sunlight* both the tert-butyl and tert-arayl hypochlorites decompose quietly with the evolution of heat, The stability of the tertiary alkyl hypochlorites is attributed to the absence of a tertiary hydrogen atom which necessitates the breaking of a carbon-carbon bond for decomposition to occur* The products of the decomposition of alkyl hypochlorites vary with the type (6). and aldehydes. Primary hypochlorites decompose to form hydrogen chloride Secondary hypochlorites form hydrogen chloride and ketones, and tertiary hypochlorites form methyl chloride and ketones. Thee© reactions are illustrated by the following equations* h Primary RCHgOCl -- ♦ RCHO + HC1 Secondary RgCHOCl — - — RgGO + HG1 Tertiary R3C0G1 RsG0 + RC1 -- — E » CHb The products of decougposition listed are principal products. Small amounts of other materials are obtained also. B. The Preparation of Alkyl Hypochlorites The alkyl hypochlorites can be prepared by several methods* The most widely used method is to pass chlorine into an aqueous alkaline solution of the alcohol* E0H ♦ Hi© reaction may be represented by the equation* Cls « JtaGH ----- R0C1 + NaGl + HgO The alkyl hypochlorites rise to the surface forming a layer that may be separated and dried with anhydrous calcium chloride or sodium sulfate. The stable tert-butyl hypochlorite may be purified further by distilla­ tion at atmospheric pressure in an all-glass apparatus* This method was was used by Sandmeyer (30*31) to prepare methyl and ethyl hypochlorites, and also by Chattaway and Backeberg (6) to prepare n-propyl, isopropyl, n-butyl, sec-butyl, tert-butyl, aid tert-arayl hypochlorites* Hanby and Rydon (19) substituted calcium carbonate for sodium hydroxide in this method* Other methods have been used for the preparation of various alkyl hypochlorites* Anbar and Doatrovsky (2) prepared tert-butyl hypo­ chlorite by adding an excess of tert-butyl alcohol to chlorine monoxide in carbon tetrachlorides 5 ♦ a boh a aoGi ♦ HgO Tk* m m authors prepared carbon tetrachloride solutions ot tert-butyl hypochlorite by shaking an aqueous acid solution of hypochlorous acid with a carbon tetrachloride solution of tert-butyl alcohol* With this 'm m method they prepared solutions of 3,3 ^3’*tsiehloro-l-metiQrlpropyl hypochlorite and ethyl and tert-butyl hypobrcaj&tes. n t h many of the. preceding methods yields up to 100 per cent were resorted* G# The Reactions of Alkyl %pochlorltes WMk only a few exceptions (Xl4.,25) all of the reported work on the reactions of alkyl hypochlorites is concerned with the us© of tert-butyl hypochlorite* In Xf31 Clark (7) reported that tert-butyl hypochlorite reacted with hydrocarbons, phenols, amines, alcohols, aldehydes, amides, ketones, esters, and ethers with some exceptions within the various classes of compounds. Acids and tdlrllea m m unreactive. Irwin and H^mion (22) found that the addition product formed in the reaction of tert-butyl hypochlorite with simple olefins depended on the solvent employed* Halohydrins, haloethers, and haloesters were produced by chlorination of olefins in the presence of water, alcohols, and acids respectively. In an inert solvent such as carbon tetra­ chloride or in th© absence of a solvent, the tert-butoxy ethar was formed* The following equations illustrate these reactions: 6 H*6H * CHR*» • a*cH» c m * » * R0C1 -§*&- eoci Etn tt Cl OH -?•**.*, + r «/jhchr '« ROH * boh 01 OR*** a*0H - m*« * a m S12SS&. ■gtomm** * mm 01 OCOH**• r*oh * 088** ■*■ soot — «*.. a*CHom*t d « M i n g, ¥ogi, and Bennlon (11) extended this mvk to ethyienic confounds containing & reactive group* Some of the compounds studied were allyl chloride, ally! alcohol, cinnamic acid, ciimamaldehyd©, and crotonaldehyde* Methanol was used as the solvemt* Other unsatur&te© that have received independent sta^y are styrene (19), isoprane (2?), methyl and ©thy! acrylates (28), <*-pinene (29), cholesterol (If), and vegetable oils (35)* Ginsburg (15) has investigated the reaction of tert-butyl hypochlorite with a number of aromatic aldehydes^ lie found that hydroxyl, methoxyl, and dlmethylamino groups activated the nucleus resulting in nuclear chlorination, whereas hydrogen, chlorine, and methyl groups activated the aldehyde group resulting in the formation of acid chlorides* Bemoic acid, p-toluic acid, p-nitrobemoic acid, m-nitrobsnssaldehyde and p-nitrobena^dehyde were unreaetive. Bxoellent yields were obtained in many reactions using carbon tetrachloride, glacial acetic acid, and 90 per cent acetic acid as solvents* 7 In a similar study with phenols Gineburg (16) found that tartbutyl hypochlorite reacted with phenols In carbon tetrachloride t© form ©«*©hlsrophenols* Grob and Schmid <1$) found that tert-butyl hypochlorite oxidized primary alcohols to esters of the corresponding acids, benzyl alcohol yielded benzaldehyde* Primary aromatic Secondary alcohols were oxidized to- ketones with mstn&eli© mid being simltaneouely deearboxyl&ted t© yield benzaldehyde* Good yields wars obtained using carbon tetrachloride m the solvent * Audrteth* Colton, and Jones have studied the formation of hydrazine from the reaction of tert-butyl hypochlorite with ammonia (3) and urea (8)* Zimmer and Audriebh (42) have reported the us© of tert-butyl hypochlorite as an ^chlorinating agent * 8 XXI BxmiMENTAL A* Apparatus A Sargent Potentiometer (U volt span) 'was used for the potentiometric titrations in glacial acetic acid* a 2 cm* 18 gauge platinum wire. The indicator electrode consisted of Two reference electrodes were usedi a saturated calomel electrode of the fiber type, and a silver*silver chloride electrode. The latter was prepared by electrolysing a solution of dilute hydrochloric acid using 1 cm. of 16 gauge silver wire as the anode* A Fisher Elecdropode (sens * * 0 *025 pa ./scale div.) equipped with 2 cm. 18 gauge platinum wire electrodes was used for the amperometric titrations. A Sargent Model XXI Manual Polarograph (sens, m 0.006U na./mm.) equipped with a twin inlay platinum electrode, Beckman #1^031, was also used for araperometric titrations. A Fisher Titrimeter equipped with a platinum wire indicator electrode and a saturated calomel reference electrode was used for some potentio­ metric titrations in aqueous solutions. A 50 ml. amber buret equipped with a Nylon stopcock assembly was used in titrations with glacial acetic acid solutions of tert-butyl hypochlorite. All other titrations were performed using a 50 ml. calibrated Sxax buret. Small samples of liquid unsatur&tes were weighed using a 0.5 ml. hypodermic syringe. Larger samples were weighed with a weight buret. 9 B# Regents and Solutions The sodium oxalate and ansenious oxide used in this work were primary standard grade. ill other inorganic reagents were either reagent grade, analytical reagent grade, or analysed grade chemicals ♦ Bakearte Qm ?* Analysed lithium chloride was assayed by the Fajans method for chloride and found to contain $9*9 per cent lithium chloride (39)* the organic chemicals used in this work were the best grades avail­ able commercially* The parity of several of these chemicals was determined, by accepted procedures, Merck Reagent phenol was assayed by a brou&nation method using standard bromte-bromide solution according to the procedure of Stone (32). It was found to be 99S per cent phenol# Eastman hydre^otneiis was assayed by the procedure of Furman and WXlae© in which the hydroquirono was titrated poientiometrically with eerie sulfate (13)* Its purity was found to be 1G0*£ per cent# Many of the unsaturates used in this work were assayed by the aoid-catalyzed bromination method of Byrne and Johnson (5). The results of these determinations are found in the section entitled "Determination of Unsaturation”. Dupont glacial acetic acid (99**1%) was used exclusively throughout this work# Glacial acetic acid free from reducing substances was prepared by refluxing 1 liter of glacial acetic acid with 20 g# (2$) of chromium trioxide for two hours in m all-glass apparatus. The acid was then distilled and $00 ml. of the middle fraction collected for use# 10 Aahytoou* acetic mtd m s prepared by refluxing 1 liter of glacial acetic acid with go ml* of acetic la&ydride {$% by volume) for four in an all-glass apparatus* h a te r* The acid m s then distilled and 5 0 0 ml. of the middle fraction collected for uae* Anhydrous acetic acid free from reducing substances m s prepared by refluxlng 1 liter of glacial acetic acid, 20 g* of chromium trioxide, and 50 ml. of acetic anhydride for four hour* in an all-glass apparatus* the acid m s then distilled and 500 ml* of the middle fraction collected for use* tert-Butyl hypochlorite m s prepared in 1 mol® quantities according to the method of Teeter and Bell (36). The crude hypochlorite was purified by distillation at atmospheric pressure in an all—glass apparatus* The purified material m s stored in srnfcer glass-stoppered bottles in a refrigerator* field® of fj g, (?1$) and 89 g« (82$) ware obtained with two preparations* The purity of the hypochlorite m s determined by breaking m&ghed ampules of the hypochlorite under 100 mL. of 5 per cent aqueous potassium, iodide solution acidified with 25 sold* of glacial acetic The liberated iodine m s titrated with standard thiosulfate solu­ tion using starch indicator* The first preparation m s found to contain 96*3 per cent t@rt~bu.tyl hypochlorite. 95*b per cent# After eight months it contained The second preparation contained 88*6 per cent hypo­ chlorite. Solutions of 0*1 U tert-butyl hypochlorite in glacial acetic acid were prepared by adding the required amount (5.U g*) to 1 liter of glacial acetic acid# The solutions were stored in amber ^lass-stoppered 11 bottles under & heed end protected from direct sunlight* The standardi­ sation of those solutions is discussed in the section entitled ^Standardisation of Glacial Acetic Acid Solutions of tert-Butyl S^ehlorits»* Other standard solutions used in this work were prepared by accepted procedures* These include standard solutions of sodium thiosulfate (biX), eerie sulfate (UO), silver nitrate {39), bromatebromide (32), and the bromlnaiion solution used for the determination of unsaturation (5)* The eerie ammonium sulfate and the ferroin indicator used in the preparation of a standard eerie sulfate solution were ob­ tained. from the 0* Frederick Smith Ghemieal Companjr* Standard pro­ cedures were used for the preparation of dichlorofluorescein (39) and starch indicators (hi)* 0* Standardisation of Glacial Acetic Acid Solutions of terb-Butyl Hypochlorite This work m» undertaken to investigate the analytical applications of tert-butyl hypochlorite in facial acetic acid. Therefore, it was of prime ia^ortanoe to establish an accurate method for the standardisation of such solutions* 1* lodine-Thiosulfate Method Several investigators (1,6,314,35) have stated that tert-butyl hypo­ chlorite liberates iodine quantitatively from an aqueous solution of potassium iodide acidified with acetic acid according to the reaction* CH3 CH3G-0-G1 ♦ GM* ghs 2HI CHgC-OH * ghs HG1 ♦ 12 The iodine can be titrated with a standard thiosulfate solution and thus the parity or ooneentration of teri-butyl hypochlorite determined, this Is the only method reperted for the assay of terMjutyl hypochlorite. In this reaction 1 mole of teri-buiyl hypochlorite liberates 2 CfiivaXenis of iodine and the normality of a hypochlorite salutim would be based on an © 9NINIVIAI3U lOOid °/c oi o z CD 0 > < EFFECT CO > CO < LU N O i o> OF TERT~BUTYL CM OF ACETIC HYPOCHLORITE STABILITY CM OF WATER ON THE 00 SOLUTIONS I. OQ ACID FIGURE 2U *5 glacial acebi© acid freed from reducing substances bat not anhydrous, and anhydrous acetic acid that was freed from reducing substances* these studies sere carried out in the same maimer as the previously described stability studies and the data were treated in the same manner also* the results are illustrated in Figure IX and the data acre contained in the Appendix* Far comparison the stability curve for 99*7 per cent glacial acetic acid has been included in Figure XX* Curve B in Figure IX represents the stability of tert-butyl hypo­ chlorite in anhydrous acetic acid freed from reducing substances* This curse has a different shape than those of solutions not freed of reducing substances* Bien compared, with curve A, which represents the stability of 99*7 per cent- acetic acid, it is m m that the initial rapid decomposition has' not occurred* However, the oversell rate of decompo­ sition was slightly greater than that of the hypochlorite in commercial acetic acid* Curve C represents the stability of the hypochlorite in acetic acid freed from reducing substance® but not anhydrous. The stability of this solution was similar to that of the anhydrous solution with the rate of decomposition slightly less* Both solutions freed from reducing substances showed m over-all rate of decomposition greater than that of the commercial untreated acid* The reason for this was not apparent* The preceding stability studies indicated that no advantage would be gained in treating commercial acid to make it anhydrous or to remove reducing substances. Therefore, the commercial acid was used in the ^ o fw ' 0> 2 X CT> < O < CD O 9NINIVW3H IDOd °/< ACID Ul 5 ACETIC < OF o STABILITY 33) and a silver-silver chloride** platinum electrode pair (20). these two electrode systems were used in this work. Using either a saturated ealomel^platinura or a silver-silver e&Uride~platiuum electrode pair, no potential m m observed m m tort* butyl hypochlorite was added to glacial acetic acid. to the low conductivity of glacial acetic acid, This was attributed 'When sodium acetate was added to glacial acetic acid, potentials m m observed with both electrode systems, With the calomel^platinum system on© drop (0*03 ml.) of hypochlorite solution caused a change from 220 imr. to 721 mv. With the «ilver~silr©r chloride and platinum electrodes a potential change from 2U6 mv, to 850 nor* occurred with the addition of one drop. the same ^proximate potential changes were observed when lithium chloride was used as the electrolyte* Potential changes of from 229 mv. 32 to 826 m * and from ISO m n to 9X0 air* were observed with the calomel and silver—silver chloride electrodes respectively, The changes were l&ien lithium chloride was used as the electrolyte, the very rapid. potential changes were- due to the presence of chlorine and net hypo­ chlorite* The observed potentials were unsteady and not reproducible* For eocawple, potential changes of 653 mv. to 9k& m * and from 6 H mv. to 8U2 mv. were observed using the silver-silver chloride and calomel electrode systems respectively under the same saperimentaX conditions, The potential changes observed with an excess of hypochlorite indicated that the pobentioraetrtc method of endpoint detection might be applicable in titrations with this reagent, 2* Amperometric The amperosaetrie method of endpoint detection alloys tm platinum electrodes connected to a potential source and a galvanometer, in the presence of a redox couple a current flows when & potential Is applied to the electrodes, Several variations are possible with this method and they are discussed in the appropriate places, With the amperometric method, of endpoint detection no current was observed when tert-butyl hypochlorite solution was added to glacial acetic acid, Potentials up to 3 volts did not produce a current flow, bhen sodium acetate m s added to facial acetic acid, small currents were observed. present* Larger currents were observed when lithium chloride was Bromide© and iodides also produced currents with the magni­ tudes dependent on the applied potential, the concentration of the t 33 electrolyte, and the concentration el* the hypochlorite. Bron&dee and iodides also yielded the corresponding halogen when hypochlorite was added. The observed currents were very steady* this method also appeared applicable to titrations using tertbutyl hypochlorite* I*. isrt-Babyl %poohlorite as a Source of Chlorine Frequent mention has been made of the formation of chlorine from the reaction of tert-butyl. hypochloride with chlorides* a reaction that is vary rapid# If a substance that reacted rapidly with chlorine were titrated with a tert-butyl hypochlorite solution in the presence of a chloride it would react with the chlorine as fast as it were formed* When this reaction was complete* the excess chlorine could be detected potentiometricaliy or ajnpsrometrically. Thus tert-butyl hypochlorite would act as a source of chlorine with the amount conveniently con­ trolled by the amount of hypochlorite solution added* This type of titration inched very promising and was investigated farttem** lithium chloride was selected as the source of chloride because of its solubility in glacial acetic acid* Other salts such as sodium chloride and potassium chloride were only slightly soluble in this solvent. Figure H I illustrates the galvanometer deflection obtained with varying applied potentials when 0,1 ml. of tert-butyl hypochlorite solution was added to 100 ml* of glacial acetic acid containing various concentrations of chloride salts* 3U 80 0.1 N LiCI 70 0.01 N LlCI 60 50 SAT'D KCI SCALE DIV. 40 30 SAT'D NaCI 20 GLACIAL ACETIC ACID -1 0 0 0.1 0.2 0.3 0.4 EMF., VOLTS 0.5 0.6 FIGURE IH . GALVANOMETER DEFLECTION WITH VARIOUS CHLORIDE CO NCENTRATIO NS IN GLACIAL A C E TIC ACID 35> f m m f i g XXX 1% in apparent that the greatest sensitivity is obtained with * O A H *§©lution ©f l i M m chloride* the galvanometer deflections were very steady iadicetlng that little or no lose of chlorine occurred either fey v o la tility or chlorination of the solvit, 0* S&ierminaiion of Uns&tur&tfon Huch ©i^has&s in this investigation m i placed on the application of tert-butyl hypochlorite for the determination of unsaturation, particularly because of the lack of good methods for the determination of this type of compound * the accepted mechanism of addition of either tert-butyl hypochlorite or chlorine to unaaturates is the same as that of the usual reagents for unsaturation such as bromine and iodine mono* chloride* Some of the typos of unsaturates with which the usual methods fail are conjugated dienes, conjugated unsaturated esters, adds, and carbonyls * It is likely that these type® would also present difficulties in this work* As mentioned earlier, the products resulting from the reaction of tert-butyl hypochlorite and an unsaturaie depend on the solvent coBpositlon, However, for quantitative purposes, this is of little importance as the consumption of tert-butyl hypochlorite would be the same regardless of Aether a halohydrin, haloether, or haloester were formed* The solvent would, be expected, to have some effect on th© rate of reaction however, Three general methods for the determination of unsaturation were investigated* These were* 36 1* An indirect method la which the unaaturaie mas allowed to m o t with m excess of tert-butyl hypochlorite in glacial acetic acid aad the excess hypochlorite determined by the iodine-thiosulfai© method* 2* An Indirect method in Which the unsaiurat© was allowed to react with an excess of chlorine in glacial acetic acid and the excess chlorine determined by the iodine~thio~ sulfate method* the chlorine was provided by addition of lithium chloride to the solution of tert-butyl hypo­ chlorite, 3* The direct titration of uns&turates in glacial acetic acid using tert-butyl hypochlorite and lithium chloride as a Source of chlorine* 1* Excess Hypochlorite Method Many methods for the determination of unsaaturatioji involve the use of an excess of reagent with subsequent determination of the excess reagent * 161th such methods it is necessary to establish the optimum reaction time and this can be accomplished by performing reaction rate studies* Eats studies of the reaction of tert-butyl hypochlorite with several unsaturates were performed to determine if this method of determination would be feasible. Several unsaturates representing different types of unsaturation ware sdected for these rat® studies* the rate studies were^ performed according to the following procedure. 37 A glacial acetic acid solution of each unaaturat© was prepared* These solutions were of such concentration that a 10 ml, aliquot con­ tained approximately 1 to 1 ,5 meq, of unsaturation. The exact concen- tration of the unsaturate m s determined fey the aeid-catalyaed broraination method, Tea ml. aliquots of the solution of unsaturate were added to 250 ml. iodine flasks containing a 25 ml, aliquot of approxi­ mately 0 * 1 H t©rt~butyl hypochlorite solution* The flasks were stoppered and allowed to stand at room temperature for specific time intervals with occasional taking* Then 3$ ml. of 5 per cent aqueous potassium iodide solution was added to each flask and the liberated Iodine titrated immediately with thlosulfate solution to the disappear­ ance of the yellow iodine color. Starch indicator was not used in the rate studies because of the rate at which the iodine color reappeared* A blank m s run with the unsaturate sample omitted to determine the amount of hypochlorite present in the 25 ml. aliquot* Starch indicator m s used for this determination, The data for these rate studies are contained in the Appendix* The reaction rate curves for the various unsaturatea are illustrated in Figure IF* In these curves* the ratios ©£ meq. of unsaturation found fey the hypochlorite method to the number of meq, found by the feromination method are plotted as a function of time* designated fey the symbol R in the figure. comparison of the several rate studies. The ratio is This allowed a more direct The meq. of unsaturation found toy the hypochlorite method were the number of meq* of hypochlorite consumed* These were calculated using the equations 38 2ooa 2. 3. 4. 5. 6. 7. VINYL ACETATE STYRENE CYCLOHEXENE 2-OCTENE MESITYL OXIDE DIVINYL BENZENE VINYLACETIC ACID 1.500— rr 1.000-5 0.500 1 0 1 I 2 TIME ,HOURS 3 4 FIGURE EC. REACTION RATES OF SEVERAL UNSATURATES WITH T E R T - B U T Y L H Y P O C H L O R IT E 39 # m Mt, * fsS., B»*B/)a(bl*nl£) » ml. ^ ^ ( a a ^ l e ) } x * «Wl» th. exception of vinyl acetate, all unoaturatea studied eonaamed an axcesa of hypochlorite. She study of vinyl acetate vac not ecmplated doe to the slowness of the reaction. She time for complete reaction varied with the different unaaturates with 2~octens requiring the shortest tlae of t m houra. All rate studies indiaated that the reaction of tert-butyl hypochlorite with unsaturates was toe slew for auialyt&cal use* It would be passible to develop analytical methods for individual unsaiun&tea using e^irioal factors to correct for tbs high results* Such methods, however, would have no advantages over existing methods for uneaturation. 2* Excess Ohlorin© Method A study of the reaction of unsaturates with chlorine was undertaken primarily to provide a comparison with the reaction of unsaturates with b®rt*butyl hypochlorite* This investigation, in the form of reaction rat® studies, was accomplished using the earn® general procedure followed in the previous reaction rate studies involving t©rt~butyl hypochlorite, the reaction of tert-butyl hypochlorite with lithium chloride was used to provide the chlorine. in The solutions of unsaturates acetic sold that ware used in the preceding rate studies ware used in this study also . They were assayed again by the bromination method. Uo Th© rati© studies war© performed using the following procedure# Twenty-five mi. aliquots of approximately 0 .1 N tert-butyl hypo­ chlorite solution were added to 250 ml* iodine flasks. To each flask was added approximately 0 .5 g. of lithium chloride and a 10 ml. aliquot of the solution of the unsaturate. The flasks were stoppered and allowed to stand at room temperature for specific time intervals with occasional shaking. Then 35 nil* of 5 por cent aqueous potassium iodide solution was added to each flask and the liberated iodine titrated immediately with thioeulfate solution to the disappearance of the yellow iodine color. Starch indicator was not used in these rate studies except in titrations of the blanks. A blank was run with the unsaturat© sample omitted to determine the amount of hypochlorite present in the 25 ml* aliquot. A second blank was run to determine if any change occurred in the amount of available chlorine after standing for a period of time. The data for these rate studies were treated in the same manner as the data of the previous rate studies and are contained in the Appendix. The reaction rate curves for the various unsaturates are illustrated in Figure V. The reaction rate studies established that the reaction of chlorine with unsaturation was very rapid. With the exception of divinylbenzene and mesityl oxide the reaction was complete in one or two hours. In all cases, however, the final value of H was over 1 .0 0 0 indicating that too much chlorine was consumed. The blanks established that there was only a negligible decrease in the amount of available chlorine after an hour of standing. This loss amounted to less than 0 *1 per cent ltl 2.000 1.500 -------( ------------$ ------ -------e ------ -------©-------- o-A 2 -------------# — - I1 ------ O — -------e -----— .------- © ------ C C l.00( 0.500— 2. 3. 4. 5. 6. 7. 0 VINYL ACETATE STYRENE CYCLOHEXENE 2-OCTENE MESITYL OXIDE DIVINYL BENZENE VINYLACETIG ACID 1 FIGURE 3E. 2 TIME, HOURS R EA CTIO N UNSATURATES W IT H 3 4 R ATES OF SEVERA L C H L O R IN E la and it is poasiblo non added* effect** it when the potassium iodide solution therefore the high result# m e t be attributed to substitution In this meiWt there * large excess of chlorine m s present the possibility Of substitutioii m s very likely. 3* 'Wrest titration with tert-Buiyl Hypochlorite as a Source of Chlorine The reaction of tert-butyl hypochlorite with unsaturatea m m too slow to permit a direct titration*: tJaing potentiomeirie endpoint detection large potential changes were obaerred when hypochlorite solu­ tion m # added to a solution of styrene in glacial acetic sold contain­ ing sodium acetate, The potentials drifted slowly and repaired several minutes to return to a stable value. This Indicated that the reaction m s Slow and was supported by the previous reaction rate data. The same ' behavior was observed using amperometrie a n o i n t detection* from reaction rate, data it appeared that the rate of reaction of chlorine with unsaturatee was rapid enough so that a direct titration would be feasible using tert-butyl hypochlorite and lithium chloride as a source of chlorine* a* potmtlometric Titration of Styrene To determine If this type of titration was possible, a sample of styren® m m titrated potentioraetrlc&lly with a standard tert-butyl hypochlorite solution. The sample m s wei#@d by hypodermic syringe into 100 ml* of glacial acetic acid containing 0*5 g» of lithium ©blonde* A Sargent Potentiometer equipped n t h platinum and silver- silver ©blonde electrodes m s used* figure ?! illustrates a typical U3 h- Ll I if LU O UJ cr >- o fO h- Ll . cn O O ^ o Z CC o => f= O < w f < p 3 tr 9 u or I— UJ a: o 2 x UJ ho Q- CL >1 _j i — o z o H 3 CD UJ I X K => cr C9 UJ u. I — CD uu poiwfiiontplo titration curve. in the Appendix, The data for "this curve are contained ®$iilii>rium was reached very rapidly after »«<»* addition of reagent and & well-defined potential change of approximately too MV. occurred at the endpoint la the titration. titration results were obtained d w electrode was need, i calomel reference Shis electrode sretera, however, did not respond «S rapidly «e that using the silver-silver chloride electrode, and the titration « u difficult to follow, *h« erratic potential values observed during ths titration were charaeteriatlo of all potentlometrie titrations performed in this work. Several samples of styrene wars titrated using potentlometrie endpoint detection. The results of these titrations are contained in Table TUI. TABUS O S POTEHTIOsfflTHIC TITRATIOM BESOMS OF STKBSS Electrode System id BOCl %QG1 gTaken Found Per Cent 3%r@ne Sid. les of styrene were titrated at room temperature and low temperatures in the same solvents used for the low temperature titrations. £L fbe titration procedure vat the same also ©accept for the addition of 1 g< of mercuric chloride prior to the addition of the sample to the solvent* A sample of styrene tms titrated in glacial acetic acid With mercuric chloride added also* The recite of these titrations are found in Table XXI. for comparison the results from Table XI hare been included in Table XIX* These are the titration results performed at both temperatures in the same solvents. TABLE XII m m o t OF MEEOORIC CHLQBXDI OH TimAXIOK RESULTS Solvent C. £41. N B0C1 BGC1 ...fr-Jto Taken Per Per Cent Gent K wb k I Styrene Brroi gl HAc (Hg) 2? 33.27 0.1032 0.1783 0,1788 90? HAc,105S Ha0 25 35,IjO 0.1033 0.1853 0.1901* 102.8 ♦3.1 90S* HAc, 10? Hb0 (Hg) 25 35.60 0,1033 0.1907 0.1915 100.1* ♦0.7 < 10 ltlj.00 0.1008 0,2273 0.2309 101.6 +1.9 90? HAo, IQ? Ha0 (Hg) < 10 1(2.10 0.1008 0.2208 0.2210 100.1 ♦O.lt 80? HAc, SO? eci* 25 lil.ao 0.0927 0.1981 0.1989 10Q.lt ♦0.7 80? HAS, 20? CCXt(Hg) 25 1*3.80 0.0873 0.1987 0.1991 100.2 +0 ,5 < 10 Wt,07 0.0927 0,2126 0.2127 100,1 ♦O.lt 80? HAS, 20? 0Cl*(Hg) < 10 lt2.10 0.1007 0.2210 0.2208 99.5 ♦0 .2 90? HAs, 10? HgO 80? HAs, 20? CC1* 100.3 *0.6 *99*7$ in glacial acetic acid at room temperature The titration result obtained with mercuric chlorid© in glacial acetic acid at room temperature was high compared -with the previous 52 results obtained with mercuric chloride absent. to decomposition, caused by mercuric chloride. This was probably due The extent of this decomposition could not be determined by rate studies due to interference from mereurlc iodide formed in the usual procedure Involving Iodine and thiosulfate. The endpoints ■were very stable in titrations where mercuric chloride was present, The decomposition was probably very slow and occurred during the titration. The presence of mercuric chloride improved the results obtained using the other solvents at both temperatures although the results were again higher than those obtained using glacial acetic acid without mercuric chloride. The presence of mercuric chloride improved the actual titrations as they could be performed more rapidly with fewer unsteady deflections prior to the endpoint. This resulted in sharper endpoints• m t h the exception of glacial acetic acid alone at room temperature, the best experimental conditions for the titration of unsaturates were low temperatur©, the presence ?of mercuric chloride, and glacial acetic acid containing 20 per cent carbon tetrachloride as the solvent. Several other unsaturates were titrated using these conditions and the results are found in Table XXIX. There was a definite improvement in the results with 1-octene and 2-octene. No change was obtained with vinyl acetate and 3-hepten© yielded poorer results. 53 TABLE XIII COMPARISON OF TITRATION RESULTS Per Gent Unsaturate * Ml. RGC1 N R0G1 g. Unsaturate Taken Round 1-Octenas 28.20 0,1013 0.1515 0.1603 105.8 123.1 98.1 2-0ctene 28.20 0,1013 0.1714-6 0.1603 91.8 9U*U 90.0 3~H@ptene 3U.7G 0,1012 G.191U 0,1721*. 90.1 8 9 .0 86,0 Vinyl acetate U3*iiO O.IGOU 0*1911+ O.I876 98 97.9 95.6 Unsaturate glacial acetic acid alone By bromination method H. Miscellaneous Oxidations 1, Sodium Oxalate The reaction of tert-butyl hypochlorite with excess sodium oxalate as a means of standardisation ha® been discussed previously. The use of tert-butyl hypochlorite for the determination of sodium oxalate was studied also. As with previous work it was necessary to use 80 per cent acetic acid as a solvent. The direct titration of sodium oxalate using tert-butyl hypochlorite as a source of chlorine was too slow to be practical. When the usual titration procedure was used, the addition of hypochlorite solution caused a large current which decreased vary ©lowly indicating a slow reaction. Therefore, indirect method® were investigated in which an excess of th© hypochlorite was present. 5L To determine if an indirect method would be feasible, the follow­ ing rate study was performed# Twenty-five ml. aliquots of tert-butyl hypochlorite solution were added to 2£0 ml* iodine flasks containing 0*067 g. (1 meq,) of sodium oxalate dissolved in 20 ml* of water and 55 ml. of glacial acetic acid* The flasks were stoppered and allowed to stand for varying lengths of time with occasional shaking* Then 1GO ml* of 3 per cent aqueous potassium iodide solution was added to each flask and the iodine titrated immediately with thiosulfate solution to a starch endpoint* A blank with the oxalate omitted was run to determine the number of meq. of hypochlorite present in th© 25 ml* aliquot. The number of meq* of hypo­ chlorite consumed for each sample was calculated from the equation* # meq* * [Ml. M a g S ^ (blank) - Ml. NagSsG3 (sample)] x N HagSg03 The results of this study are found in Table JOT* TABLE JOT REACTION RATE OF SODIUM OXALATE WITH EXCESS tert-BUm HXPOCHLORITE Reaction Time, Min* Blank Ml. NagSaOg* 'Sample Difference 1 22.76 13*61 5 22.91 15 30 22.91+ 12*79 12.8$ 22.91 12*75 1*5 60 22.9U 23.07 12*79 12.90 90 22.91+ 12.76 ^Normality ■ 0,0986 Meq* Found 9*15 10*12 0*902 10,lit 10*16 1,000 1.002 1 0 .1 5 1,001 10*17 10.18 1.003 0*998 1.Q0L & St appeared that the reaction of terb~butyl hypochlorite with sodium escalate waa quantitative with a reaction time of 15 minutes* The high results obtained with longer reaction times pointed to the possible deoo^poeition of chorine* The chlorine would be formed by the reaction of the excess tert-butyl hypochlorite with the chloride formed as one of the products in the oxidation of sodium oxalate* To determine if the high results were due to this decomposition, a rate study was performed on the decomposition of chlorine in 80 per cent acetic acid* In the previous rate study there were approximately 1 meq. of excess tert-butyl hypochlorite and 1 meq* of chloride. Therefore, the rate study was carried out using their quantities of reagents. The procedure used in this rate study was identical with the previous reaction rate stu^r except for the quantities of reagents used* Ten ml, aliquots of hypochlorite solution were added to 250 ml* iodine flasks containing 0,0585 g* (1 meq*) of sodium chloride dissolved in 2Q ml* of water and 70 ml. of glacial acetic acid. The flasks were stoppered and allowed to stand for varying lengths of time with occasional shaking. Then 100 ml, of 3 per cent aqueous potassium Iodide solution was added to each flask and the iodine titrated immediately with standard thiosulfate solution using starch indicator* for the blank a 10 ml, aliquot of hypochlorite solution was added to 90 ml, of acetic acid containing m sodium chloride* The data are contained in fable Xf. The perccent decomposition has been calculated on the basis of the volumes of thiosulfate solution used in the titrations* 56 Percent doeorapoeition « x kjo. TABLE XV BBCOHPOSITICfH OB' CHLORINE DJ EIGHT! PER CENT ACETIC AGIO Reaction Time, MXa,. MI. S»#,Oa i l S ^ r'r':rn,'VIirrl K ^ S ' :J ",r SlSSSS®® P(H, Cent Beeowposition I 8.52 8.52 0 .00 0 .0 0 5 8.52 8.52 o.00 0.00 15 8.52 8.52 0 .00 0.00 30 8.52 8.51 0 .01 0.12 1*5 8.52 8.50 0 .02 0.23 60 8.52 8 .U9 0 .03 0,35 90 8.52 a.us o.01* 0.1*7 ^Normality m 0.0986 Tha data in Table XV verifies the decomposition of chlorine in 80 per cent acetic acid and accounts for the high results obtained. If the reaction time were limited to 15 minutes* the decomposition ’would be negligible* Several samples of sodium oxalate were determined using this procedure with a 15 minute reaction time* The results are found in Table W E * $h© results in Table W E indicate that this method is applicable for the determination of sodium oxalate* 57 TABLE. XVI DETERMINATION OP SODIUM OXALATE WITH EXCESS tert-BUTXL H3POCHLGRITE «• MX. Na.S.0 a......,,„ Blank Sample Difference . BaaCfl0 . .......... Taken Found 22,82 11 ,98 10.81* 0.0716 0.0716 22.82 11.52 1 1 .3 0 O.O7 I46 0.0717 22.82 13.19 9.63 0.0635 0.0 63 6 22.82 5.91 16.91 0.1119 0.1117 22.82 10.61 1 2 .2 1 .0807 0.0807 ^Normality » 0,0986 2* Benzaldehyde the reaction of tert-butyl hypochlorite with benzaldehyde and sub­ stituted benzaldehydes lias been studied by Ginsburg (15) • He found that excellent yields of the corresponding acids or acid chlorides were obtained, the reactions were rapid at room temperature in 90 per cent acetic acid, tert-butyl alcohol, and carbon tetrachloride, fhe high yields and moderate conditions reported by Ginsburg prompted, an investigation into the analytical possibilities of the reaction of tert-butyl hypochlorite with benzaldehyde. ^he direct titration of benzaldehyde using tert-butyl hypochlorite as a source of chlorine was too slow* Mien the usual titration pro­ cedure was used the addition of hypochlorite solution caused a large current flow which remained steady indicating a very slow reaction. 58 Indirect methods were tried using both excess hypochlorite and excess chlorine. Sample* of benaaldehyde were added to %$Q ml. iodine flasks oontaining 25 ml# aliquot* of tert-butyl hypochlorite solution* One flash bad 0*5 g. of lithium chloride sided* The flasks were SXlowed to stand one hour with frequent shaking and then the excess hypochlorite or chlorine was determined in the usual manner* The results of this experiment are contained in fable XTO* TABLE X U ! G i m m m OF BM2ALDSHIDE Sample Differaraoe g.Beoa^ahyde Taken Found Per Cent Pound Hypochlorite 21.73 21.52 0.0. 0.0750 O.OCttl 1.1*6 Chlorine 21.73 21.52 0.21 0.1037 0,0011 1.06 formality « 0*0986 The results indicated that the oxidation of benzaldehyde was very slight under the experimental conditions and no further investigations were made with benzaldehyde * 3# Phenol Ginsburg (16) and Clark (7) have investigated, the reaction of tertbutyl hypochlorite with phenols* The reactions were very rapid at room temperature resulting in excellent yields of the corresponding orthosubstituted ehlorophenols* bith a large excess of hypochlorite various polysubstituted chlorophenols were obtained. S9 Samples of phenol were 'titrated amperometrically in glacial acetic acid using tert-butyl hypochlorite as a source of chlorine* The first additions of hypochlorite solution caused small deflections which returned rapidly* to zero« Subsequent additions of reagent caused larger deflections that returned to zero slower* Finally a point was reached in the titration where the deflection m s almost steady* This occurred beyond the volume of reagent corresponding to raonosubstitution of phenol. It was apparent from this that chlorine m s too reactive to be used in the determination of phenol* The amperometric titration of phenol with hypochlorite solution alone m s investigated using several solvents. Mien the reagent was added to a solution of phenol in glacial acetic acid no deflection was observed* MLih sodium acetate present the addition of reagent did cause a deflection which decreased slowly indicating a slow reaction* The same behavior was observed with acetic acid containing $ per cent water and no salts, The titrations using both of these solvents were too slow for practical use. In acetic acid containing 10 per cent water and no salts the titration m s more rapid and additions of reagent caused deflections which returned to zero in one or two minutes. Near the endpoint corresponding to monosubstitution the deflections became larger and returned slower, Past the equivalence point the deflections decreased very slowly indicating that further substitution m s taking place. However, the titration could be performed by reading the galvan­ ometer deflection at a predetermined time after each addition and then plotting the observed deflections versus ml. of reagent. Figure V U 60 2.0 SCALE DIV. 3.0 1.0 0 0 5 ML. ROCI SOL'N FIGURE Y U . A M P E R O M E T R IC PH EN O L WITH TERT~BUTYL 10 T I T R A T I O N OF HY PO C H LO R ITE 61 i® & plot of titration results using a 90 seconds interval after each addition before reading the deflection* found in the Appendix* The data for this Figure are The volume of reagent was determined by drawing a line through the deflection points beyond the endpoint and finding its intercept an the reagent axis. Table XVXX contains the results of several titrations performed using this procedure* TABLE XFIH m p m o m n x o dotation results of phenol ^001 g. Phenol ... Found. Taken 7.75 0.0993 0.0360 0.0362 100.6 5.52 0.0993 0.0258 0.0258 100.0 9.55 0.0890 0.0ii2X O.Oijl? ........... HI. R0C1 Per Cent* 97.1** *99 • by bromination From Figure ?XI It appeared from the results obtained that the reaction proceeded according to the equation5 + R0C1 ♦ ROH This titration procedure m s not practical with larger samples of phenol because of the time involved in performing the titration. This procedure 62 also failed when sodium acetate was added to the 90 per cent acetic acid solvent . In this case the titration resembled that in which the hypochlorite was used as a source of chlorine. Indirect methods for th© determination of phenol were not investigated because phenol reacts with iodine thus interfering with the general method. U. Hydroquinon© Th© reaction of tert-butyl hypochlorite with hydroquinon© has not been investigated previously* It was studied in this work primarily because the hydroquinone-quinone system is one of the few organic redox systems available for investigation (9). When hydroquinon© was titrated amperometrically using only glacial acetic acid as a solvent, no deflection was observed with applied potentials up to 3 volts. A rapid oxidation did take place, however, as the solution turned yellow when the reagent was added. Hydroquinon© could be titrated in glacial acetic acid using tert-butyl hypochlorite as a source of chlorine. curve* Figure VIII illustrates th© resulting titration fhe data for this figure are found in the Appendix, fhe titration curve in Figure VIII is characteristic for redox systems in which both the oxidised and reduced forms govern th© current flow (33). Throughout most of the titration, equilibrium was attained rapidly. Wien the endpoint was approached additions of reagent caused large deflections which returned slowly to steady values. The endpoint should have been indicated by a large steady deflection caused by the formation of chlorine. However, an endpoint could not be obtained due to the unsteady deflections which returned to zero. 63 6.0 SCALE DIV. 4.0 0 5 10 15 ML. ROCI SOL'N 20 FIGURE 3ZHT. A M P E R O M E T R I C T I T R A T I O N OF HYDROQUINONE W IT H T E R T - B U T Y L H Y P O C H L O R I T E A S A SOU R CE OF C H L O R I N E 6h The titration ‘ was not stoichiometric and a large excess of reagent was used* Similar titration results were obtained when hydroquinon® was titrated in acetic acid containing 10 per cent water* hydroqulnone was also titrated using glacial acetic acid containing sodium acetate# The addition of the sample to the solvent caused a large deflection that remained steady. This was not observed in the titration using lithium chloride but it was observed using 90 per cent acetic acid as a solvent . In the latter case th© titration curve was similar to that obtained using lithium chloride, Wien hydroquinon© was titrated in glacial acetic acid containing sodium acetate, a different titration curve was obtained. This is illustrated in Figure IX, data are found in the Appendix* The Equilibrium was reached rapidly through­ out the titration and th© endpoint was steady. The titration results were still high but much better than in previous titrations using other solvents. Th© oxidation of hydroquinon© by tert-butyl hypochlorite can be represented by the following equation} + E0C1 A frtnrt.ijir equation could be written for th® reaction in which the hypo­ chlorite is used as a source of chlorine, Xt is probable that some chlorine m s formed during the titration of hydroquinon© with tert-butyl hypochlorite alone and that the high results were due to the SCALE DIV. 65 2.0 CALC'D E.P. 20 ML. ROCI SOL'N FIGURE I X . A M PE R O M E TR IC T I T R A T I O N OF HYDROQUINONE W I T H T E R T - B U T Y L HYPOCHLORITE 66 chlorination of guinea©. Th® much larger error observed with titrations In ‘ which the hypochlorite was used as a source of chlorine supports the fact that It was chlorine and not hypochlorite that was responsible for the high results* The explanation for the titration curve obtained using glacial acetic acid containing sodium acetate was not apparent* I? S0HMARX 67 w mmmr ferilary butyl hypochlorite can be used as an analytical reagent far the determination of a limited number of organic cozspounda in nonaqueous solvents. Solutions of tert-butyl hypochlorite in glacial acetic acid are reasonably ©table and decompose at the rate of 0*1 per cent a day* fhe solutions can he standardised easily and rapidly. fhe indirect determination of unsaturation was net possible using an excess of tert-butyl hypochlorite eolation either alone or as a source of chlorine* Reaction rate studies with several unsaturates established that with terfc-butyl hypochlorite the reactions were too slow and an excess of reagent was consumed. Reaction rate studies using an excess of tert-butyl hypochlorite as a source of chlorine established that the addition was rapid but that an excess of chlorine was consumed* fhe direct titration of unsaturates with tert-butyl hypochlorite was not possible due to slow reaction rates* Using the hypochlorite as a source of chlorine it was possible to titrate unaaturatas amperemetrically or potentiometrically. Good results were obtained with styrene and fair results were obtained with divinylbensene when glacial acetic acid m s used as the solvent* With all other unsaturates tested the results were either high due to substitution or low due to slow reaction rates* 68 Efforts t© improve the titration results ware unsuccessful. High results were obtained, with titrations at low temperatures using acetic acid containing 10 per cent water or 20 per cent carbon tetrachloride as solvents, fhe use of mercuric chloride as a catalyst also failed to improve the results. Sodium oxalate could be determined accurately in 80 per cent acetic acid using an excess of tert-butyl hypochlorite and determining the access* Fhenol could be titrated araperometrically in 90 per cent acetic acid but the determination was limited to small samples and was not vary accurate* lydroquinone could be titrated also but an excess of reagent was used yielding high results* Sensaldehy&e could not be determined directly or indirectly because the reaction was too slow. iLXSEEuanmE coted 69 LITERATURE CITED 1* Aribar, K*, and Boatrovsky, X., J. Cham. Son*, 1Q9U-1101* (195U). 2* Aafcay, M., and Dostroroky, I*, J. Chem. Soc., 1X05-8 (195h). 3* Aadrleth, L # F., Colton, 1., and Jones, M. M*, J. Am. Chera. So©*, 26, 1UT8#3X (19a) . li# Brass, B*, Anal# Gham., 21, 11*61-5 (191*9). 5* %3m®, R* E. Jr., sad Johnson, J. B., Anal. Chem*, 28, 126-9 (1956). 6. Chatiamy, p* B*, and Backeberg, 0, G., J* Chem. So©., 123. 2999-3003 (1923). ?. Clark, B. P., Chem. Bess, ^ 265-? (1931). 8. Colton, B», Jones, M. M*, and Audrieth, L. P., J. Am. Chem. So©., 26, 2572*1* (1951*)* 9* Gonant, J. B*, Chem. Her*, J, 1-1*0 (192?). 10. Bt* Bois, H* B., and Skoog, D* A*, Anal. Chem,, 20, 621*-? (19U8). 11. Emling, B. L., Vogt, R. R*, and Beimion, G. P., J. Am. Ohm. So©., 162^5 (19ltl). 12. Freedman, R# W,, Anal* Ghem*, 28, 21*7-9 (1956). 13* Ftirman, If#, H*, and Ififtllftss, J* H# Jr., J# J®. Gheja# Soc•, 52, 11*143-? (1930)* 11*. Pasco, B,, and Masante, C., Gazz. ©him* ital., 66, 258-61* (1936), C. A., J|, 1777 (1937)* 15. Ginsburg, D,, J. Am. Chem. Soc., JJ, 702-1* (1951). 16. Glnsbarg, B., J* Am# Ghem* So©*, 21, 2723-5 (1951). 17. Glnsbarg, B., J* Am* Ghem* So©*, 2*U 5U89-91 (1953). 18* Grob, G# A., and Schmid, H# J., Heir. Chim. Acta*, J6, 1763-70 (1953). 19* Hamby, W. £*, and Rydon, H* H*, J# Ghem* Sec., lli*-5 (19U6). 70 2 0 . M tw raxk, 0 . H ., 7 h « l* , Mlehig«a» Sttoe OniTWuity, 1954. 21. BlMnrasJc, 0, H.» tod Stona, K, 0 „ Anal. **♦ Cham., 2J, 371-3 (1955). 0» y.» tod Hannion, 0. F., J. to. Cham. Soe., 6£, 858-60 23. ls*ie, J, S., and Bradstroat, R. B., lad. Bag. Chem., Anal. Ed., SI* '307*00 (1940). 2lt. Luoaa, H. J „ and Pressman, B.Ind. Eng. Cham., 140-2 (1938). Anal Ed,, 10, ~ 25. Huaante, e „ and Fasco, C,, Gaaz. chin. ital., 66, 639-4*8 (1936), c* *•» it, 3459 (1937). ~~ 26. Novotny, J „ Chem. liaty, lj8, 1865-7 (1954), C.A., Ijg., 4443 (1955). 27. OroohniR, W., and Mallory, R. A,, 4. to. Ohem.Soo., 72, 4608-13 (1950). 28. Raynold*, D. B,, and Banyan, W, D. C. A., }£, P 91*74 (1950), 29. Bitter, «J* J*, and Ginsburg, B*, J*Am* Ghera. Soe*, 72, 2381-h (1 ^ 0 )a 30* Stmdmyer, T*, Bex%, 18, I?6?~9 (1885). 31* Saadmeyer, T., Ber., 1£, 857-6? (1886)* 32* Stone, K* G., MBeterralnation of Organic Compounds,11 pp, 123-U, McGraw-Hill Book Company, Inc,, Sew York, 1956. 33. Stone, K. 0*, and Soholten, H* G., Anal* Chem*, 671«*h (1952)* 3k* Taylor, M. 0*, Saemillan, B* ©*, and Gammal, 0* A*, J* Am. Chem* Soo., J$U 395-1*03 (1925)* 35* footer, H. M., Bachman, B. €*, Bell, E* W», and Coma, J* C*, Ind* Bng* Chem*, jy., 81*8*52 (191*9)* 3 6 . Teeter, H* M«, and Bell, B* W*, Org. Syn., JJ2, 20~2 (1952). 37* Tomecek, 0., and Heyrovsky, A,, Collection Czech. Chem. Common., lg, 997-1020 (1950)* 38* Tmecdk, 0., and Valcha, J*, Collection Czech. Chem. Common., 16-17, 113-26 (1951-2) 71 39. Wllard, H. H,, Furman, B. H., and Brisker, C. B,, "ELenents of ftianttfcatlve Analysis," M>h Bd,, pp. 121*9, D. Van Noatrand Company, Inc,, Princeton, 1956. 3M&** w * 237 -W.. UX, Ibid.. pp. 26^-6. Ii2. ZlaBB»r, H., wed Aidriath, L, P., J. An. Qhea. See., j£6, 3856*7 (19514. APPEHDH 72 0A1A FOR FIGCRE 1 Stability of tert-Butyl hypochlorite in Glacial Acetic Acid time, Baya ^ E0C1 For Cent R0C1 Remaining 0 2U .60 0.0993 100.0 1 2ft.5ft 0.0991 99*8 2 2ft*ft9 0.O98? 99*6 7 2ft*37 0,098ft 99.1 1ft 2ft*26 0.0979 98*6 21 2ft.08 0.0972 97*9 28 23*9ft 0.0986 97*3 formality m 0*1008 73 Stability of tert**Butyl J^ypocblorite in Ninety Far Cant Acetic Acid Time, Days KL. Ife^JIJa* NS0C1 Per Cent ROC1 Remaining 0 26.63 0,1075 100,0 1 26,5k 0.1071 99.6 26.k9 0.1069 99 ,k 26,15 0.1056 96,2 25,8k 0.10k3 97.0 21 25.59 0.1033 96.1 as 25.37 0.1021 95.0 7 *Horn»lity - 0,1008 ?1* Stability of tsrt-Butyl Hypoehlorlto In AnhydrouB Aoatie fold ML. * * # & * Haoei Per c«nt HQC1 0 23.73 0.0949 100,0 1 23.43 0.0945 99.6 3 23.51 0.0941 99.1 ? 83.17 0.0927 97*6 lb 28.54 0.0902 95.0 ax 22.05 0.0882 92.9 28 81.52 0 .08 a 90,7 T±m9 Dagr* *Nonaalifcy « 0*0999 Remaining 75 MTA FOB FIGURE H Stability of tert-Satyl Hypochlorite laa Aaahydrous Aeetie Acid Freed frcaa Beducing Substances Oayc IQ.# NstjaSjjPa ^BQGl Per Oesst B0C1 Rerriainlng 0 «3*& 0,091*1 100*0 1 23M 0,0939 99 #9 2 23 M 0.0939 99.9 7 23 #35 0.093U 99.3 lit 23.17 0,0927 98.6 21 23,01 0.0921 97.9 28 22.83 0,0913 97.1 *H0MBlity - 0,0999 76 Stability of tert*&tttgrl J^pochlorit© la Glacial Acetic Acid Freed from Reducing Subataneee time, Days mi a n * M1- %*sfisPa © 21*.16 0.0967 100.0 X 21*.15 0.0966 100.0 2 2H .ll* 0.0966 99.9 7 21*.©6 0.0963 99.6 11* 23.90 0.0956 98.9 ex 23.73 0.091*9 98.2 as 23.57 0.09U3 97.6 *Ko*»*aXty - 0.0999 For Cent R0C1 Remaining 77 BAfA PCS FIGURE III Galvanometer Beflection with Parlous Chloride Ion Concentrations In Glacial Acetic Acid Applied Potential folia NaCl 0*0 *4*0 O*.0I r.^m. ■*5*8 «*»#* # S * t: •*« * 0*02 -1*,6 : *** *N# 0*03 0*04 ***» 0*05 #«•* 0.06 .. «Mfr to** 0*01 N Lid L1C1 —6,0 -5.1 -4.9 1.4 3.8 12.2 7,6 20.1 12.3 16.9 30.4 40.8 20.4 24.0 48.2 —2,4 -1.2 1.0 •* * * 2.2 *# ** MUMS 4.8 *M » -5.7 1,6 28.4 33.0 58.2 66.0 76.0 30.6 36,4 81.0 66.0 88x2 49,8 66.8 62x2 87x2 88.2 46x5 57x5 78x5 52x10 57x5 68x5 54.5 53x2 63x2 73x2 80x5 76x10 89x10 62*5 71.0 82x2 93x2 91x5 53x10 52x20 59x20 0*0? *H W ****■ 0*08 *M *. ■ **# - 0.09 *W * * * * 0*10 *-5*6 2*2 11.9 0.2 -4*2 6,1 18,0 9*1 0*3 o.U *5*0 *4*8 29,6 16*7 41.5 0*5 0*6 *•4.7 •4*1 53.2 65,4 23*5 31*0 0*7 0*8 -3*9 —3 *8 **3*6 77.8 38*5 46*2 90*3 51x2 -3*3 57x2 0*9 1*0 HIT UC1 **« * 6.4 8.2 10.2 64x10 **0*10 ml* ©f 0.1 H hypochlorite solution added to 100 ml* of solvent* 78 TUBA m FIOORE 17 Enaction Hate of 7inyl Acetate alth tert-Butyl Hypochlorite 2 23.66 20.69 2.97 0.301 0.11*2 9 23.66 20.80 2.36 0.290 0.139 15 23.66 20.36 3.10 0.311* 0.1k7 30 23.66 19.38 k.08 0.103 0.18k US 23.66 19.18 k.k8 Q.USU 0.202 60 23.66 18.0k 3.62 0.369 0.26k 120 23*66 16.69 6.97 0.706 0.362 180 23.66 13.23 8*k3 0.85k 0,508 2)j0 23.66 Ik. Ok 9.62 0.975 0.671 *HoiTOality « 0.1013 1.1)06 neq. found by broaination 79 of with tert^Butsrl hypochlorite rM*m Un«aturate E «■**** 15 n ►36 23.40 4 .9 8 0.5 0*3143 a.6i 6.77 0.686 0»i*66 2Q.89 7.49 0.759 0.516 35 8 ,9 6 0*908 0*617 . 9.92 1.005 0 ,6 8 3 16.97 11,33 1.148 0*780 18 1*6 60 I6.l6 1.230 14.65 13.65 1.383 0*939 13,81 14.49 1.1 0*997 15.70 1.; 1,081 1,662 1 *129 l.< 1*131 iao .35 300 .35 11.91 m 0, # found by broisination 60 Rmurtlon R*te of Qjrelohexena with tert-Butyl Rypoohlorita * !toi Min* ~Wmk“ !&aJ&^SaS^ " Difference ideq. tfnsatnrafc® Found*** R X 21.97 11.1*3 10.5k 1.053 0*727 ? ■21.97 7.73 lk .21* 1.1*23 0*582 15 21.97 7.95 lk,1*2 30 21.97 7.30 Ik.6? 14*66 1*012 kg 21.97 7.03 Ik .9k l*l4$>6 1.033 60 a.9? 6,77 15,20 1.515 1*01*6 120 21.9? 5.81* 16.13 1.611 1.112 180 21.97 5.51* I6.k3 1.61a 1.133 21# *1.97 5.51* 16.k3 1.61*1 1*133 m 21.97 5.5k I6.k3 i.6ia 1*133 360 21.97 5.52 16,k5 1.61*3 1*135 ^Hormality *• 0.0999 **1.1*1*9 meq. found ky breminattoa Q.^5 81 Reaction Rat® of 2-0ctene with tert-Butyl Hypochlorite Time, Kin, Meq. Unsaturate Found** Ml. 11aoSqO< Blank Sample B 1 26 .51 1 7 .6 0 10.91 1.105 0.809 2 28,55 16.95 11.60 1.175 0 .8 6 0 9 28.55 1 6 .7 6 11.79 1.19U 0.87k 15 28.55 1 6 ,3 6 12.19 1.235 0.90U 20 28,55 16 .08 1 2 .hi 1.263 0.92U 27 28.55 15.95 1 2 .6 0 1.2 76 0.93lt U5 28,51 15.27 13.2U 1.3ltl 0.982 60 28,51 lit. 86 13.65 1.383 1.012 90 28.51 lit.38 lit.13 l.lt31 1.0lt7 120 28.51 llt.2 6 Hi.25 l.ltltlt 1.056 2lt0 28.51 llt.1 8 lit.33 1.1(52 1.062 ^formality * 0 *1013 1.367 raeq. found by brominatioii 82 Reaction Rate of Mesityl Oxide with tert-Butyi Hypochlorite Meq. Unsaturate Found** time, Hin* Blank 1 22.1*2 19.39 3.03 0.305 0.322 7 22.1*2 15.81* 6.56 0.659 0.696 15 22.1*2 ll*.59 7.83 O .787 0.831 30 22.1*2 13.11* 9.28 0.933 0.985 145 22.1*2 12.10 10.32 1.037 1.096 60 22.1*2 11.52 1Q .90 1.096 1.157 120 22.1*2 9.02 13.1*0 1.31*7 1.1*22 180 22.1*2 6.91 15.51 1.559 1.61*7 2I4O 22.1*2 5.61* 16.78 1.686 1.781 300 22.1*2 U .67 17.75 1.781* 1.881* 360 22.1*2 1».58 17.81* 1.798 1.891* HI. Na»S„0,* Santis Difference formality - 0.1005 ^0.9U? meq* found "by hromination a 83 Rate of BtTinyXbanaene with tert-Butyl Hypochlorite 1 7 22,71 82.71 35.19 3*52 0.35U 0.301 17 .1*8 5.23 0.526 0.1*1*2 15 22.71 16,82 5.89 0.592 0*503 30 22.71 IS,18 7.53 0,757 0,61*1* US 22.71 1U.3U 8.37 0.81*1 0.715 6® 22,71 13.55 9.16 0,921 120 '22.71 H.6U U .07 1,113 0 .91*6 180 22.71 10*12 12*59 1,265 1.076 21*0 22.71 9.29 13.1*2 1.31*9 1.11*7 306 22*71 8.66 lit.05 1.1*12 1*201 360 22*71 8.53 Hi.13 1.1*25 1.212 *Waality * 0,3005 ^ 1.176 m q * jMdt by brominatlon " 0.783 81* Reaction Rato of finylacQiic Acid -with iart-Butyl Hypochlorite BX&Dk m * jj*ws «o «* Saiaple Difference Meq. Onsaturate fWBaa** K i 22*53 20.1*9 2.01* 0.205 0.155 7 22.53 18.88 3.65 0.367 0.278 15 22.53 17.79 l*.7l* 0 .1*76 0.361 30 22.53 16.22 6.31 O.63I* 0 .1*81 1*5 22.53 11*.91* 7.59 0.763 0.578 60 22.53 13.80 8.73 0.877 0.665 120 22.53 10.1*2 12.11 1.217 0.922 180 22.53 8 .5 6 13.97 1 .1*01* 1 .061* 21*0 22,53 8 .1*0 11*.13 1 .1*20 1.076 300 22.53 8.38 11*.15 1 .1*22 1.078 360 22.53 8.36 11*.17 1 .1*21* 1.079 « 0.1005 **1,32© meq. fcund toy bromination 65 DATA FOR FIGURE V Reaction Rate of Vinyl Acetate with Chlorine Time, Kin. as* 1 22.1*8 8 .1*6 11*.02 1 .1*01 1 .021* 7 2 2 .1*8 8.26 11*.22 1 .1*21 1.038 15 22 .1*8 8.15 111.33 1.1*32 1 .01*6 30 22.1*8 8.15 H*.33 1 .1*32 1 .01*6 1*5 2 2 .1*8 8 .11* 11*.31* 1.1*33 l.o!*7 60 2 2 .1*8 3.08 11*.1*0 1.1*39 1.051 120 2 2 .1*8 8.02 11*,1*6 1.1*1*5 1.056 180 2 2 .1*8 8.09 li*.39 1.1*36 1.050 21*0 22 .1*8 7.67 11*.61 1 .1*60 1.066 300 2 2 .1*8 7.82 11*.66 1.1*65 I .070 360 2 2 .1*8 7.78 ll*.70 1.1*69 1.073 Saiaple - Difference *Normality • 0,0999 **1.367 m *. found by bromination Unsaturate Found** S 86 ft©action Rate of Styrene with Chlorine '•flW'Ti'i uni uimvmmui * Difference Unaaturate Found** 6.38 16.78 1.700 1.151* 23.66 5.90 17.76 1.799 1.222 15 23.66 5.53 18.13 1.837 1.21*7 36 23.66 5.5U 18.12 1.836 1.21*6 60 23.66 5.57 18.09 1.833 1.21*1* 130 23.66 5.I16 18.20 1.81*1* 1.252 Blank Ml. MaaS. r' SampS 2 23.66 7 Min. ^Normality * 0*1013 1.U73 meq. fotmd fey bromination B 87 Reaction Rate of Gyclohexens with Chlorine Mao, Min. r* HI. Saxaple 1Siffarenee " 1 ifoi™'"' Pns&tarato Found R 1 23.21 5.17 18.01* 1.802 1.245 1 23.21 4.68 18.53 1.851 1,279 15 23.21 4.72 18.4? 1,847 1.276 30 23.21 4.68 18.53 1.851 1.279 45 23.21 k.m 18.56 1.854 1.281 60 23.21 4.57 18,64 1.8® 1.286 120 23.21 4.51 18,7© 1.868 1.290 18© 23,21 4.50 18.71 1,86? 1,291 240 83.21 4,44 18,77 1.875 1.295 300 23.21 4.37 18,84 1,882 1.300 360 23.21 4.34 18,87 1.885 1.3® ^Normality * 0.0999 l,i4*8 found by branfnation 88 E&aetion Eat® of 2-Octen© with Chlorine Heq. fim © , Wm* Ml. Ha«S j a * . . ' . S5£3T~ Saunpla S tfi'a ra n e B U n s a tu ra ta F o u n d**' R t 22.04 7*72 1U.32 1.431 1.960 1 22.04 7*64 lli.Uo 1.439 1*066 XS 22.04 7*71 Hi.33 1*432 I .061 30 22.04 7*72 111.32 1.431 1.060 hS 22*04 7.55 Hi.ii? 1*448 1.073 60 22.04 7.4? 14.55 1.454 1.077 120 22 .04 7*35 14.69 1.468 1*08? 180 22.Oil ?.21i 14.90 1.479 1.996 21;0 22.01i 7.27 14.77 1.476 1*093 300 22.Olt 7.25 14.7? 1*478 1.095 360 22. Oli 7.2? 14.74 1.473 1.091 formality ■* Q.Q999 **1*350 maq* found by bromination 89 Reaction Hate of Mesityi Oxide with Chlorine Meq. Unsaturate Found R lk.k2 l.kkO 1.523 8.36 1U.80 l.k79 1.563 23.16 8.0S 15.11 1.510 1.596 30 v 23.16 7.87 15.29 1.528 1.615 kS 23.16 7.36 15.80 1.578 1.668 60 23.16 7.03 16.13 1.6U 1.703 120 23«l6 6.3k 16.82 1.679 1.775 180 23.16 5.92 17.2k 1.722 1.821 ZhP 23.16 5.50 17.66 1.76k 1.865 300 23.16 k.9k 18.22 1.820 1.92k 360 23.16 5.03 18.13 1.811 1.91k |a Time, Min* Blank 1 23.16 8.7k 7 23.16 15 MX. Ha?Sa0 ^ Sample Difference ^Normality * 0*0999 **0.9U6 meq. found by broiaination 90 Re&ebton of IHviiaylbenaene vith Chlorine tfneeturete Found** X 23.26 10.00 13.26 1.325 1.125 ? 23.26 9.23 14,03 1.402 1.190 15 23.26 8.56 14.70 1.469 1.247 30 23.26 8,26 15.00 1.499 1.272 JUS 23.26 -8 .05 15.20 1.519 1.289 60 23.26 7*95 35.31 1.530 1.299 120 23.26 7.79 15.47 1.546 1.312 180 23.26 7.61 15.65 1.563 1.327 21*0 23.26 7,62 15.64 1.563 1,327 300 23.26 7.63 15.63 1.562 1.326 36© 23.26 7.63 15.63 1.562 1,326 i«i> "Kormaltby * 0*0$W **1.1?8 meq* found by brondnatlon 9X Enaction. Hate of VlisyXacetie Acid with Chlorine B Difference Me^i Unsatnr&te Found** 5.8? 12,98 1.296 0.975 22.85 9.5? 13.28 1.327 0.998 IS 22,85 9.H7 13.38 1,337 1.005 30 22.85 9.HO 13.H5 1.3HH 1.011 US 22,85 9,35 13.50 1.3H9 1.01H 60 22.85 9.30 13.55 1.35H 1,016 120 22.85 9.22 13.83 1.362 1.02U 180 22,85 9.16 13.69 1.368 1.029 2U0 22.85 9,19 13.66 1.365 1.026 300 22.85 9.19 13.66 1.365 1.026 360 22.85 9.1U 13.71 1.370 1.030 time, Min, Blaric" 1 22.85 t ^Normality « 0*0999 ^1*130 meq, found by bromination 92 BATA FOR FIGURE VI Potentt©metric Titration of Styrene with tert—Butyl Hypochlorite as a Source of Chlorine MX. S0C1* Ml. H0C1 S.M.F.(iw.) 0.0 627 26.0 736 2.0 61*7 27.0 7U1 h.O 663 28.0 721 6.0 672 29.0 728 8.0 680 29.5 738 00.0 688 30.0 71*8 12.0 71U 30.1* 737 1U.0 73U 30.6 761* 16.0 ?Uo 30.8 913 18.0 729 30.9 973 20.0 698 31.3 991* 22.0 716 33.0 1007 2U.0 726 33.0 1013 37.0 1017 *Normality * 0.1033 93 BATA FOE FXOGEE V U Araperomeiri© Titration of Fhenol with tert**Buiyl Hypochlorite ux« aota* Galv. Bafl., Scale Blv. Ml. E0C1 Qalr. Defl., Scale Biv, 0,0 0.0 7.0 0,0 x.0 0,0 8.0 0.0 2,0 0.0 9*0 0.1 3.0 0.0 9*5 0,3 U.o 0.0 10.0 0.5 5.0 0.0 10.2 0.7 6.G 0*0 10.5 x . k 11*0 2.7 Normality * 0,0890 Sample weight * 0*01*21 Calculated endpoint * 10.03 mX* 94 BATA FOE FIGURE VIII AjRpercmetric Titration of Hydroqainone with tert-Batyi Hypochlorite a® a Source of Chlorine aswan**■TfftasBBg.'Tt..asa ta. Kxa* Galv. Befl., Scale Biv. HI. R0C1 Galr. Defl,# Scale Div. 0.0 0.0 10.0 5.3 1.0 2.8 11.0 5.1 2.0 3.8 12.0 4.7 3.0 4.4 13.0 4.2 U.O 4.8 14.0 3.4 S.o 5.1 15.0 2*4 6.0 5*3 16.0 1.1 7.0 5*4 17.0 0.2 8.0 5.5 18.0 0.0 ?,Q 5.4 Normality * 0.0880 Sample weight • 0.0603 g. Calculated endpoint * 12.40 ml. 9£ DATA FOR FIGURE IX AiHperometric Titration of Hjydroquinone with tert-Buiyl hypochlorite Ml* KOGl* Salv. Dafl., Seal* Hr, hi.aoci Galv. Defl., Scale Dir. 0*0 6.5 lo.e 4.5 1*0 5.8 U.O 4.4 2.0 5.5 12.0 4.2 3.0 5.3 13.0 3.8 4.0 5.1 14.0 3.2 5.0 5.0 14.5 2.5 6.0 4.9 14.8 2.0 7.0 4.8 14.9 1.1 8.0 4.7 14.93 5.6 9.0 4.6 14.97 7.4 *Kormallty m 0.0839 Saraple weight • 0*066? Calculated endpoint » Hu5X i«l»