A WIDE RANGE, EXTREMELY SENSITIVE HEGH FREQUENCY TlTRSMETER Thai: for tho Dogm of M. S. MQCHSGAN STATE COLLEGE Arthur H. Johnson 1954 IGAN mm}\uxuxfiimfiflmx 31293 007 1 SI NW » LIBRARY ‘Michigan State I ' University PLACE IN RETURN BOX to remove this chédtan from your record. TO AVOID FINES Mum on or below date duo. DATE DUE DATE DUE DATE DUE ll jUUE LL :l MSU Is An Affirmdivo Action/Equal Opponunity Institution _ cWflnS-DJ .——_—-—'fi*7 . u .___‘A-. 44 In VIBE RINSE, 121711:me SENSITIVE HIGH FRNUERCI TRRMER 3? Arthur H. Johnson A THESIS Submitted to tho Balm]. of Gradum Studies of Michigan State College of Agriculture ad applied Scienc- m partial fulfillment of the nquirmnta ' for the degroa of K1313! OF mIE'iHC'S Depmnt. or CImintry 1933.. 1:.CKRCHLEIDQ‘I m S The author to greatly indebted to Dr. Andrew 71min): ulna ldndmu and patient narration ”do the coupletion of thin Waugation possible. Grateful acknowledge!“ 1: also due to Dr. Elmer Lounger md Dr. Kmneth Stone for helpful magmatic” and encouragement, to Hr. Frank Betta for his friendly co- nnotation 1n the shop, Hr. Loni: Sharp. for m- assistance with the drains and photography, and Mr. Raymond B. Jotuoon for hi. tit-sly undue... 4“an iwmm ”vim W > .7 i new 11 £3 5mm Tho actors of tbs row at ugh frequency titration instru- lslts dssoribod in current lit-orator. was studied. Tho investigation included instant-Ms in clinch the sol-pic solution vessel was placed bow-ca tho pistes of s capacitor typo coll snd 1mm. with the suplo solution vssscl placed in the coil of s recount circuit. 1 A the offset on tbs mponso 01' than instruments of couple solution toupsrcturs ohms, dilution, ohms in liquid incl. change: in col]. puss-torn, cm supls solution concoct-"tic: were dctcmimd. Thou studios confined findings of sorlior imstigstions. i m. truly condoctmtrio high troquoncy atrium vss doubpcd. 7h ass of s single two loop imusd of s mltituru coil, in sidition to ssintcining s critical separation bots-no the titration vessel “11 md tho 100p, reduces tho distributed capacity to on shsolntc mm. lament response with this arrangmt is dependant on conductivity changes and independent of dielectric constant changes in tho smplc ”lotion. Changes in solution competition are indicated by chocgos is oscillator tuba grid current. Instmcnt psrtornnoo as tested with titrstions of mucous solo- tioos of ivdrochlorio, sulfuric, and boric acids and hydrogen peroxide with audio: hydroxide. Evidcnos of polybcsic centralisation was observed in sulfuric acid and borio acid titration. In this work the first successful high frequonoy titration of borio soid was oooocplidzcd, iii I‘lllls‘llllulllllllllllll and furthsnsors proscnts for tho first tins svidcnco of mutt-slin- tics of the second and third roplsosabls hydrogen ions. The sulfuric said titration. substantiate earlier inconclusive ovidcnco of poly- bssio mtrslisstion. t successful high frequency titration of thrss non-ml hydrochloric said sith tour normal sodim hydroxide we carried out, imticcting that tho m instrumot say bs nssd tor conductivity studios in s concen- trstion raglan horstofors unsttsimd. ‘l'hs oasis winch tho titrstios cum lines ion: at tbs squisalsncs point obtainsd in this study for boric said titration sxsctly duplicate tbs snails obtained in ths olsssicsl oondcotmtric borio said titration“ cmiod out by xolthoff. I'm this it is {19wa that the response at tho m mm is pursly mistivs . iv Tibial: (E Cour..m5 Page mih'Di"3?I§E!OOOOOOODOOI§DUOOOOOOWDOOOOOOOOIOOIO00¢...00.0.0»00.0.0 1 Stawmnt of §3rot’13m000300OOOIOOOOOOOOOOOOC0......0......-IOOO 2 TEb‘jEIOOOICOOOOaOIOO9.00.00.00.9‘..’.'.".....".........'.....’. 3 btPh-tl... h” ‘L...........¢......g.......ssscocoa-osgsOOsOsossOoOOOI 20 Frar’zrgtivn 0‘: RiggiwrszSCOOOCOOUO....DGOOOOOOOOICCCOOOIII00.... 23 Incidsntol Instrumentation.................................... 21 The Parallel }-.'ec=onr.nt Cimuit Titrimotor...................... 21 The Promo-nay Mommflcg Inotmmnt............................ 2-3 T1” E’fitiffi Ranga TitrhwaPOOCQOO'COOOOOOCIOCUOODOOOOflQOO'J.O...O 1‘9 In Hodifiosti-Jn or the Wide hang-3 ‘l‘itrhaotor..............,..., (:5 Titrations filth quucncy Rewiring»; Earthwork... ........,... '3'": Titration "1th tho Vida Ringo Titrimcter....... .. ... ....... .. 72 PNS‘RIUI‘B for t‘ 1“ must :djactmont of tm w'ido Rangjtc TimmnterOOOUOOOCDOOOOOOOIO'ODOOIIOOOOOOOOOOOQOOCsOOOOOOOO 73 Polmgrcph Adjust-.1: mnsc ”hm Load in Commotion ‘a‘iith the ‘w’i-io £81139 iritfi' ‘eroIDsoossssosisssOscoals-CocosstoosssososOsO 78' Perfonaamc of tho Parallel licsonzmt Circuit Ti't.rimetcr....... ’30 Portommoo of the Frequency Measuring Titrimter. .... ......., Pl Porfommcc of tire ‘5ch Range! ‘i‘itrimctor...................... 9’) or '- pr! '3 CCE""'I-"‘-'I)“’Jssocos-osesssossssssssosssssssssosoosoooass-soo-ooosos 1L3 LI? :1" ”Ln" CIT Dosssssssoossssosssss-ssOssoossossssoosossssssssss 1n‘5 I. _’T‘ fig i'ETPSR‘JIKsOOOssssci-osossos-u0sssoosoososssossssssassocsoOuOOOOIIOoss 1"" Illllllllllll'sll'll LIST OF 1.2.31.3 HELL"; 19.5.83; 1. Frsrgucnoy motility 01’ Frequency Motor Oscillator... ........ II. wit-1c Range Titrimotor cdj‘zstmnts Pertaining to Sonsi tivity canaa.‘O'COCOOOOCOOOO'COCOOOO.00"...IOOOOOOOIOIODOICOOQ¢DOO III. iadjustmonts of Ko‘fiificd “wilds Kongo 'i‘itr‘imctor Pertaining to {hnflitiflty Sumgao-oooossoossosos=Obo-osooostooososoI060... I’v’. Acid-Bass Titrations with Frequency Roaming moment..." 7. Precipitation Reactions with Frequency Removing Instr-moat. VI. Acid-Bass Titrations with Frcwcncy measuring Instrmont.... VII. Precipitation Rotations with Frequency Measuring: flatworm. VIII. Titration of 5333. with kWh...”........................ IX. Titrations of K21 nth NsCB................................. 1. Titrst’iom Of 5333., flth Ha’jassOsssssssosOOQOIso-OOOIfiUOOOOO 1:2 61 71 86 8-7 88 89 97 98 99 II. Titration: of H380. with 3:63..........,.,....,.,,.,.u”... 100 XII. Titr‘tion' or Eff}. flth 35089....sc.00000s0ssssssosssssOssss 1'31 vi llllll‘llil'll rm? 1: .11 '7‘? 4:1! 1. 2. 13. 1h. 15. 16. 17. 15. 19. .20. "r 2'" Th“ F: .V‘ L: ’I) U:- ‘ *‘VJN’ DI." I a." Magnitude uni phzw angle of tha 1:th mace of the sis-min in Fig.3” 2 53 I {Mia}! 01' fM‘ilii3my-OGCOco¢c-¢not-docooo Hesiztamo ma! “th9 mm“ of a pair-mu]. circuit a a timfltlon 0.! «freq‘ufency...gg.g.ooogcanuflaotilCOOOODOOOC 50133151}. 0331118“? Circuit.o...at...OOGOOOOIQCoouoOOOOOOID Voltam mi current relations eastmg in m «Saginaw “2121133. 81953151} 5‘5me Ganjitions‘.ogga.o 9. 9.0.0.0... O .00..... Swhmatia diagram of almantary high fmwlflmy titrimim‘. inflates 93919me in ear}; L133: Mvrm‘ncy titrations...” Prdbs dntails............................................. (insulator circuit of fz‘aqummy manuring Snatnmentuu... Pow-3r supply circuit...“.................................. Tap vim: or main ctmasis..."nu......................... Batten vim of main chassis"............................. (310333;; of 0:311 and 953 tabs ancfmts...................... Cloaaup of coil and tube atdald 1n pagition............... Feedbwk capacitcreu..................................... (3.) Gail mummy, 3) Base plats with coaxial mmactorc. Titration nasal inserted into petition inside: of band: or capacity tme can.I00...IIOOOOOOiO¢OIIO~OtifOIOIO‘COOOOOO Capacity t-y-pa can with app-432' 32213ch assembly in position. Capacity cell plugged into martian 1n lick of main cl‘aa818000.000l.0COCO...UOOOOQCC‘COCOOOICIOOOCOOOO’OOOOOOI Baa-z: plat-e vuit‘a female comdal receptacle! plumes! into malt-ion on main chgafl'OOIuOInc..0.0QOOIO$QOOIOIIQOOQOOQC Feadbgck capacitor: in mutton on ban-e plum.......... ... v11 : (M. V1 LIST (I? FIi‘:L’£1:3 «- Continuai ’21. Titration Yer-5353.91 inserted into position in 12.5) as. .- -+. U¢:I7mll~y cmOOOOCOOOOOOOOOOoOOIDOQUOO'OOQOOCCDOOOOOOOOO 22. 1.?er sl'dald assembly of 120 Inc. cayaicity cell Blowing 63590611401" Flaws.oogo..aoooou.-CIIOIOIOOOIOoOOOtOOOOO'0. 23. Turin-eta:- frequency stability at. 12.1} 183................ 23s. Influeme of collation bmmmtam changes on frequency" 25’. Irzfluianm cf «shame: in liquid Laval an fraqammy......, 26. Ezfluanm of chmgmo in liq-.1111 13ml and dilution cm fmqu‘ancj-otococoon-octooooooococoocoo-OOOO0.00000”u" 2?. &eph 02mm»; alums-tic?! of majxarzaes due ta dilution and change in 11«"r.Lid 12:31 in the *3le range 1-230 to 111‘ n10.OOOOOOOOCOOOOOOCOUOOOIO.OOOCOCOOOOOOOOOOOCI..C9. 23. Emmiuflty cum of 12*?) no. frequency magnum-mg inat'I‘LWVntqltoO'0.00.0000to...o-ooaououoooooooQOOQQOOv.0 29, (Emilia-bar circuit of wide ram-,0 titrimetar...........u 33. Vida range titrimémr with cover mawmd from 0311 “3-3:;ny slowing; "" traction vessel in position in loop... 31. “Kid current humming circuit 32. Wide range: titrimter sensitivity mm:................ 33. Wide range titrimatar sensitivity cums...-..-..uu.u 31;. New}. position cm“... 35. V-sawl position tun 3:3. Effect of fixed bias on Immunity; cums.............. 3?. Batman of wide range titrinatar to cimngaa in liquid lewl.’DOOOOOOOOOOOOOOOOOiIICCOOOOO0.00.00...O.cal-00.0. 38. Response of wiia range “Water to chant?" in liquid lwgl ma dilution.DOOOOOOOOOOOOIDO_OC000.000.060.0000000 ' 39, Sensitivity curves of muffled visit: ranger titrimt::r.... viii PAGE; ho h) 1;} 1:5 he. 53 59 60 5-2 62 66 67 6-7 6:8 LIST {IF F1}!!! 33 :- Confiludgd P3565 1.3.“:3n3‘ti'dt; carves: of noziitiea vii a rang! etitrimeter...” arrange {air-mater, mim'ww h, and asamiatad £51338 881 up for minors-3110118....nooocounoOCOQoOuOOOOOO W}, app 1:2. £53, 120 me. {half wave. line; (3) Amt-1214) frequency meter; )Ihat‘udt m is}. ”9-3 ‘iarrrm tum filibuster; (3)) Bi}- i lemma me traquancy mnibar; (T ) Cam”). mus M301 7353-». verve avatar; (b) loops 1, 2, a .d 3 for vim rwga “Wtel‘ goooogooonccootoootouoooCUOOOOOoDCI-OOOIIOOOO'I it: L3. Tunisian of 53793. with 5803...“........................ ah. Tifmabion or me with Ewan...“....................... .‘5. Titration of £3550; with14:331.”.......................... 1.5. Titration of 153334 with 133.352."..uu.................... L7. flimti'm of 1131 with E95311".............................. L3. Titration of 331 with flax—UH.............—.................. L9. ’Eiaratian O: [39'3”3 With HEDHOOOIOOOOOOOOOCOOOOOOOOOOOOOCO SO. ‘iiration of E3303 with 2536 H flaming wir. tense of mu- traliutian or second and £211. M rejnlmahla tunings!) ion: 31. Titration 0: Hit. ELM: flag-Jan...a...600.096.000.0000000000 ‘0' 5 9 LI 7h ,4 u" enum- 5“ f3.“ ~g‘u’ p} r , b5" : . J- R W. . .1 -1 1.» maroon-anon In the denomination of tho and points in high trogucncy titra- tion, tho capl- oclntion in a nasal is incorporated a a component or a rcconant circuit. Chung" in tho concentration of ion- present in tho colution change tho electrical proportion of the circuit. Change. in m ionic concentration: may bc dctcctod through changcc in tho tnqucncy of an occillatcr, if the resonant circuit in the frequency dctcrnining clcncnt of tho ccoillatcr, through chmgca in the grid or plate current. of the occillator, or through change. in call capacitance. Tho ail of decimal-c of high {mommy titrinctcra baa boon to obtain a roaponu which 1! a function of the conductivity of the colu- tion only and nor. truly upmcntativc of chanson in tho concentrations of the ions in tho colution. Host of the papers publictnd on high (my titration since it. introduction in 19146 by Jonson and Pal-rack (10) have bum devoted to tho ccnctructional details or inctm- ncnto wrportod to ovorconc curtain difficulties coccuntcrcd in th- application at tho instrument dcocribod by Jon-on m Parrcok (1,2,6) . It Qpcara that individuals in olcctronico generally are biased in preferring on. circuit to othorl and in a narrow nanncr dctcnd tho lot-it- 0! thin choioc. It in bclicvod that this accountc for tho variety of inctmnt nodal- that hm appeared. The results obtained Ilth any om instrument or a clan arc for all practical purpose- the one as those obtained with another and inetrmonteticn is e nutter of individual preference. in e recent book (it) Lingone points out that most or the cited applications of the method are titreticns which can be performed as well or better by the ordinary conuuctancc method, and that the greater miricinn, coupled with the usual curvature or the titration lines requiring neaeurencnts very near equivalence points are distinct dis- advantages. Lingene'e observations accurately sun up the relative nerite or the nethod when viewed from the standpoint of work reported in the literature to date. The historical upsets of high frequency titretione have been revived by meouu (9) and e very nonplcte bibliOgrepky coaaipiled. Statement of Problem Il‘he discussion which follow is e reeult of e study madertekem (l) to construct tried high frequency titration apparatus with the objective of improving their performance and of elucidating the nature of the response end, (2) to construct s new highly sensitative, wide range titrineter which resulted from a new approach utter a more criti- cel evaluation of all the factors effecting instrumental response. Characteristice of the instrument were evaluated and titratione per- formed to deter-inc whether some of the disadvantages eecribed to the method had been overcome. Theory pertinent to the instruments constructed is presented. T $133312" Kl «III’ ill I. I ,‘II' II| TILE-Ii! Figure 2 (22) chow schematically a parallel circuit made up of a capacitive branch and an inductive branch. The resistance a in a function of the lone in the circuit and is due to the resietance of mating vireo, the coil, and the mniatmce reflected into the circuit by the load. The essential properties of the circuit are its resonant frequency to, it! «lectiVlW Q. end it. characteflatlc impedmce Z. The impedance in a vector quantity having both Homicide and phone. angle. For pnrpoeee or discussion, the resonant frequency is that frequency to that satisfies the relation wL.__1.... (1) W0 vhf. w - 211' f, L in the coil inductance in beam, and C is the capacity of the condenser in fax-eds. The eclectivity 0, of the circuit is given by the relation {1- ---- (2) The impedance 2 is given by the relations (3., w 1 z :w" :. numb-:73) (3b) At the resonant frequency we I. e 3%? (1e) and equation 3e mducee to z . 131%.”). u.) end equeticn 3‘0 rcducel to z W “I“ The curve- ot Figure 1 (22) e'hov the legnitnde ad pbeee angle of impedance ee e function of frequency. The moment frequency of the circuit in Figure 2 with the veluee of 0 end I. given ie 1000 kc. at reecnence, thiepedenceie eteeeadmendieequaltoQtieeethe reactence or either brmch et :0, and the phase angle ”of impedance 1- eerc. At trequenciee below reeonence the pheee eagle of inpcdmce ie negative end lower in magnitude than et rename. it frequenciee ebcve renounce the phase eagle of impedance ie poeitive end of lower nami- tude then et reecnence. The circuit ie inductive when the pbeee eagle of induce ie negative end cepecitive amen the phone angle or in- pednce 1- poeitive. ’ Il‘he Medea” of e parallel circuit can be broken up into reactive end reactive commute. Figure 2 (22) chow the reeietive enn reective mate ee e function of frequency. The reeietence vex-ice such in the ”me any ee IZO IIO ] \ IOO / X"“~IMPEDAN¢E WT}: I25 90 \ 80 I] 70 . I 4 / ***\--IMPEDAN0E 1%.. 75 60 '2’ \ 2 // \\ x 50 l \ 8 30 “##A 60 3.1" g f / PHASE ANGLE‘iRI-uzs/ {3“ “J 20 40 m ‘E // "“ ~~~ \ 5 - // PHASE ANGLE 19-: 75 8. IO 20‘ O 0 20 // 2 I 40 _, / 60 a: / ' / 0 I_._—-——‘" 970 980 990 I000 IOIO IOZO KILOCYCLES FIGURE I. MAGNITUDE AND PHASE ANGLE OF THE IMPEDANCE OF THE CIRCUIT IN FIGURE 2 AS A FUNCTION OF FREQUENCY. -3 onus xno . IMPEDANCE,- ICU ”CL o=u25-« I00 90 LL- . QOOOISSpE‘" so I I * 70 RESONANT F=IOOO KC. o=7s-~ 60 50 /r / / C-“RESISTANCE 4O 30 // \\ \\ 20 \\ u/ \ IO . ‘ \Q 0 . IO 0% 20 6‘9.“ ‘gfl‘fi' 30 . k/V‘“ Mom 40 50 /-----o= .25 970 990 IOIO I020 KILOCYCLES \ FIGURE 2. RESISTANCE AND REACTANCE COMPONENTS OF A PARALLEL CIRCUIT AS A FUNCTION OF FREQUENCY. dcee‘ impedance. The reactance cum shame a 3mm inductive react- ence at a frequency below reecnance equal to tau-W), and a madman “punitive reactance et a frequency chm rcecnsme equal to fond/2Q). it memence the reectance cum peace: through eerc, the resistance curve paeeae tlmugh its neflmgmfi themefcrc, at reacnance the parallel circuit ie equivalent to a pure racism-am equal to the charac‘tcric'tic impedance of the circuit. Ounce ee chem in Figvmce 1 uni 2 are known ea reecnance curves. The cell! used in high frequency titer-hectare ere of two typee. One ie canetructec so that the solution in the dielectric material be- tween the pletee at a condenser and is connected ecrcee the tuning condenser of the parallel circuit. Ancflnr cell type places the salu- tiec uthic the field or the coil along ite exie. In either one, the eolutioe new reflect cepecity or resistance into the tamed circuit. Tb effect on the electrical paper-tin or the perellel circuit can be deduced by exnining the remence cume cf Figuree 1 end 2. in immune in 3 will lover Q (equation 2), a lamr Q will result in a broadening or u» reeonence m (Figure 1). and lcuer the inedence, (equation 3e, equation 31:, and Figure 1). An increeee in line current will be detected when R is increeeed. mother effect or increased 3 ie a decreeee in the pheee angle or iepedance. Thie will Dealt in e eligbt ehitt in frequency than the parallel circuit in in- cea'pcreted in en cecilletcr. Thie point will be diecueeed in greater detail under millatcre. If the ecluticn in the cell reflects e capacity change into the perellel circuit, the meoncnt frequency of the circuit will change (equation 1) displacing the curves either up or dam slang the frequency exie. Therefore, when the parallel circuit is mic e part of an oscil- lator circuit, e change in frequency will b-c dctcctcd if the dielectric conetcnt of the salutiun changes. The fact that e change in the dialcctric constant of e solution will reeult in e frequency change is chvicue in the care of the capacitor type cell. than”, vhcn e coluticn in in the coil of the parallel circuit the cituation ie elightly. different, and the reason for capacity effecte nay not rug-acct iteclf. Every coil has eceocieted with it e distributed capacity an e result of dielectric etreee between various pm.- of the coil. This distributed cepecity ecte u though it was lunped ecrcee the terminal: of the coil end is in effect connected acme- the tuning condenser cf the parallel circuit. A change in the dielectric constant of the eoluticn changcc the value of dietributed capacity ccrcee thc coil and result: in e um: resonant frequency. The condition: for rceonence given by equation 1 etill hold, but it met be neutered that C in the cm: of the capacity of the taming condom:- end the value of dietributcd capacity cecccietod with the coil. If the cepccity cf the tuning condcmr ie C; end the distributed capacity cf the coil in 0,, equation 1 may be rewritten cl “ii-W (5) Since th- pnrallcl circuit in only one part. of the complete oscillator circuit, the maponsc of high frequency tibrimctcn to changes in aolution compositicn are not fully axylainablc on the basin of Mn pmportial of the: prune). circuit. clone. To be completes, the dimension must be extended to include the conditions that. must ba anti-tied in order to promote mataimd cacillatiom in a typical ”cinder. Figure 3 in a ”fanatic dingnn of the Colpitu oscillator circuit. Tb parallel resonant circuit. he! I. in parallel with the levies ambi- mtinn o: C; and 0,. Th. "cum tube in nblu to act a an oscillaim- mKh its ability to aplity. the pom input required by tho grid in Inch 10“ than tho mun-d output. Therefore, a porfion of the output power uy be fed back into my grid circuit. and animation will talc. place. the focdback in the 601.91%“ circuit is provided to the grid cir- cuit by applying to the grid that portion of the voltage developed acrou tbs parallel circuit. that. appear! across 0‘. In the caries commotion at C; and c. both condenser- vill ham the am charge Q at any inamt. Thin charge Q is not. to be confused with the Q or selectivity of the parallel circuit. The capacity of a condenser in infirm! u c -% (6) what. 0 in th- capecity in farm, Q tbs: charge in cculaubu, and V the potential ION“ the platen. Since both consensus hm tin um charge 10 F5030 m0._.<.....=0wo ”—..—.5400 .m mane—n. J Ir a:- o +m lull/bung 0mm c . v 6.“: V: (7a) v1 - mg; (71:) Equation Tb above that feedback may be varied by changing the ratio of C, to 01, the excitation increasing with smaller win» of C‘. The condition that met be satisfied in order to maintain euc- teined oscillations in on oeoilletor is that the alternating current generated by the 1mm tube oecilletor hm a frequency such that the voltage ddch the generated oscillatioue apply to the grid of the tube ie exactly 180 degreea out of phase Iith the oscillation of the equi- "lent plete voltage (23). These conditions are aetiefied in u» caee of the Colpitte oecilletor when the parallel circuit ia ma to offer a capacitive reactance to the accreted frequency. Referring to Figure 2, it will be me that the generated frequency will be higher than the recount tummy of the parallel circuit on defined by equation 1. The operating point of the oacillator on the impedance curveoftigurelwillbe thepoint atmichthe phaee angle afie- pedence ie of the proper value to aatiefy the conditione outlined above for auetained oecillaticne to take place. The oecilletor edJneta iteelf mtcnatically to then conditiona. In the dieouadon of the parallel circuit it wee pointed out that an increeee in R which occurs with an increaee in the conductivity of a eelutin in high frequency titration, reenlte in e docreaee in the phase angle of impedance and in onier to compensate, for this change the 12 oocillctor will adjust iteclf to a new frequency whore the Operating conditions are eeticficd. is change in the value of the capacity in the parallel circuit will upset the Operating conditions of the oscillator end e frequency chift will be necessary to restore tho conditions once again. Vixen the frequency changca of a vocmua tube oscillator arc mcmr- ed, coma problems arise. One ia to Icpct'nte the frequency shift dam to changes in dielectric constant which dot-amines the sec-.mt of capacity in the circuit from the frequcccy shift due to changae in conductivity which determine. tin mmt of resistance in the circuit. In an inotmnt in which the parallel circuit and associated cell are not included in the circuit of en 036111ch, the Bcpcrction of? . capacitive and reactive changes is: Quite eimple. Examples of such instruments ere than of Hall end Gibson (6), and Fujiwara and Hcyuhi (5). he principle and method of mamwcmcnt involvod in the latter circuit ia discuss-ed elceuherc (20). The curves of Figure; 1 our! 2 era obtainfl by thin nethod. The parallel circuit is tuned to resonance at the beginning of e titration in the application of this type of inetmcnt. The parallel circuit therefore Ictiaficl the cmiitiona of equation 1. Increases in cell capacity can be compensated for by roaming capacity free a uric able cepecitor placed in parallel with the cell capacity. “cording to equation 5.1: C. increeeca by en uount Ac, 0; can be decree-ed by an amount. A c and resonance an be matured. the change of oepecity 13 4 c an be ouluatcd from a calibrated dial mulled on the rotor or 0,. Usually mm is indium by a unadm voltage wading on a new: tube '01thth placed across the teminals at the parallol cir- cuit. Sine- thn impadmca cum in flat at tits point was ditriaulty in determining the exact point of resonance may arias. Small changes in capacity my 1m b. undetectable. The aplituda or the voltage gamma an" the coil is a func- tian of the Q of the circuit. Changes in voltage reading-a my be aux-Mud in mm or mmm. In gemrnl, the Maw or the mtlnd than mplied to high mamas: titration in such loss than the. mama or other nothodl. Furthmm, the valtage appliod t0 tin 1' parallel circuit mat be 1m 01‘ hmurmica of the hmdmtal Man-nmy. it romance thl nix-cult inpuimoe in high to the Mutants]. comp-mam of tha applind voltage, but in 10' to my bar-onion. Cmquently, ban-min mats will emu high line emu-onto that I111 In): the all]. linn mm duo to the {mammal cosmonaut. lo nation it ”do by Fujiwara md Reynold (5) flatlnr or not their oscillator was free of lam-mania. m wimiplu cumml m for “panting resistive and capaci- tin emporium. mama].- for aunt-able chins” in must frequency ad Q of a par-1101 cironit m not included in an emulator circuit do net apply when tho parallel circuit in part of thc oscillator circuit. is pruriaully pow out, the partllol mat in the Colpittl oscil- lm in mind to be resonant to a frequency slightly higher than the fltp'ot signs]. frsquonoj of the oscillator. Restoring tho frequency of tho oscillator to its original output frequency otter o frowonoy shift has comm-rod by adjustment of a alumina; canaoity compensates for the froqmoy Shift due to both maistmso mi capacity. Other factora that influonoo tho output tmquonoy such as oh man in plots '13}qu wltago, grit! excitation, and grid bias are also oatzponoatod. Promxonoy changes ore tlnroi'oro tin mault of tho inmootion of many varia’L-wloo. Tho omgxonrmt do. to a olwngo in to diolactrio oonatant of the solution is practically impooaiblo to dot-Mm. Oscillators may be ltabilizod to union than inoonsitivo to vario- tiono in tube charootoristioo (15) which muli ohmliry thing's Umwimt, but whether a true separation of tho variables of capacity and resistance are momliohod would bo Open to dob ate . Manors , it in conceivablia that a solution may show a dielectric constant ohmgo Wing to iron-moo the output Maquonoy oi’ an oscil— lator and a cmmotivity chengs tending to door-e we tho output frequency, moultirg in a not ohmgo of zero (7). Roturmng to the schematic diagram: or the Colpitto oscillator circuit of Figaro 3, a manta:- R; is comzactod from the grid of the tub. to ground. Before oscillations start them is no volume appliod to the grid, and thoroforo no grid current. The bias on the tube is zero and a lame plate current flow. Tho initial surge or current though the tube whoa tho cathode reaches the tamporotum at which electron mission begins, not: up an alternating ourmnt in tho parallel 15 oimit and m alternating voltago aorooo it. Foodbaok of part of m voltago to tho grid drivoa tho grid pooitivo with mopoct to the oatlndo. moon-om on attractod from tho cathode to tho grid and ova-rout flow through tho rooiotor R‘ oomnly called the grid-look root-tor. Tho voltage amp acrou tho roaiotor nakoo tho grid nogativo with tomcat to tho oathodo. Tho voluo of tho grid biao io tho product of tho avorogo value of tho grid current and tho ulna of tho grid- loak noiotor. to tho uplitncio or oooillotiono buildo up tho bioo inmuoo and owntuall: o atoady otato ia ottained when the grid bioa ond tho uplitudo of tho oooillationa main oonotmt. Tho voltago and current rolationa oxiating in an oocillotor under otoody ltato condi- tiono ». ohm in ugm-o t (23). Tho instantanoono valuo of plato voltage in tho m of tho plato apply wltogo ad tho alternating voltage donlozaod botvoon tho plato and oathodo, “gm-o ha. Tho inotantanooua valuo of grid voltage io tin III- of tho aid bio. voltogo and tho wltogo dovolopod lemon the toodbaok capacitor C; m otthodo and aid by tho ours-oat in tho turd circuit, Figaro Lb. Tho alternating ploto-oothodo voltogo and altomating add-oothodo voltago on 180 dogrooo out of phooo. Tho grid iadrivonpoaitivoforapuiod of tinloaa thantho poriodotahaltoyolo. Thoplotooumnt mdgridourrontflowin pals“, Figural ho and M. Tho plate curl-ant puloo to longer that tho grid mat pulao. Tho tubo oonduota oa coon oo tho inotantanoouo arid voltago ia alight): Ion pooitivo than cutoff on tho upward part 16 ’ALTERNATING PLATE-CATHODE VOLTAGE VOLTAGE APPL'ED I INSTANTANEOUS P ATE— AT E T To PLATE / L C HOD VOL AGE A L /,MINIMUM PLATE VOLTAGE VOLTAGE APPLIED I ,NAXINUM POSITIVE TO GRIO :z’ . GRID POTENTIAL I ’I‘ B / \ x: :I T /L l I ozmsommu IQ: >m02w30mmu “.0 .CDOEO mOP4mm3m mmBOm .m mmDGE il' 4.. ~12: 1P if 3m FIGURE 10, FIGURE 11 . TOP VIEW OF MAIN CHASSIS. BOTTOM VIEW OF MAIN CHIIVSSIS, 32 33 FIGURE 12. CLOSED? OF COIL AND 955 TUBE SOCKETS, FIGURE 13. CLOSED? OF COIL AND TUBE SHIELD IN POSITION. 3h .mmoaomzzoo M’£;,Q WWW 4784 FM. DIAL READING 4783 FIGURE 27. I05 IIO II5 I20 TOTAL VOLUME (ML) 5 IO I5 20 ML. H20 ADDED 'GRAPH SHOWING ELIMINATION OF RESPONSES DUE To DILUTION AND CHANGE IN LIQUID LEVEL IN THE VOLUME RANGE I00 T0 II4 ML. h? A sensitivity or woman mm was obtained to toot the concen- trction tongs in which the inltnment momma. flu sans tocImiq‘co as used by others was employed (2 .3,II .7 ,1”. Initially tho "cool was £111.93 with 125 :1. of distilled water. Ono ml. increments of s 1.0 I! social clam-ids solution more unified and tho frequency changes recorded. The sonoitivity cum, Figure 28, mo obtained by plotting tho froquoncy motor dial realms against the logarithm of tho sodium chloride con- centration. The curve is s typical one for frequency manning instru- ments rewrtod earlier by others (2,3,1; {1.19). 11-. m- boon slam (2.3.1:.749) that u the abscissa was the logaritIn of tho specific resistor-Ice of the ”dim chloride solution instead of its concentration, tho cw would molar to any amt-ms oloctrolyto plscod in tho Imus coll (it tho one frcqmucy, sad it would bu masonry to obtain respons- omen for our. than om electrolyte. It follow. that tho pocition of the Mom of tho curve on the abscissa and its «slope is s faction of the fmquanoy, tho coll pox-oe- motors, tho sclmt, no the ionic strength of the solution (2,3,II,7,19). It. is evident that o titrimotcr of this type has adequate sensi- tivity to two!) certain limits that m find once tho Operating frequency and coil porouotcrs m soloctod. To pox-tom a succocsful titration color than confltiono, tho specific corvtmtivity of the solution must be adjusted so that time endpoint will f 9.11 somwi'xcm flthln this limits ahom by the mitivity curve. Tho coll parocotors om variable to s limited dogma and are partially determined by the mount of loaflng the oscillator can 118 .hZMZDEhZ. @Zmzmlsms. >ozm30mmu. .02 ON. “.0 m>m50 >._._>_._..mzwm 4042 >t¢<402 o_.o .mN mmnoi _0.0 053V omh.‘ 05¢ NO¢ 'W '3 SNIOVBH 'IVIO 1:9 with-tad and um maintain sustained oucillatdona and th- tatal capacity pox-niacin: acme tho particular inductama in tha parallel circuit (22,23). u the apex-nun; frequency 1a momma, minuty umuummmummummmm,mtm man! the «11 plat" not to nduoad accordingly dumb W» m over-all ”with“: at tin apparatul at that higher cowl-int“!!! (19). Th. «nutmléamlTeauldbauuduptoéomnbutin order-tonal!” amqumyofmm. tbs canplata ma hadtoba Induced to that am 1!! 1151.111 22. The "Me mam" lielativaly few hammta had been 36:25th in which the: ach— tton was placed in a. maul in tha field a! the coil of a par-1:11.91 resonant cirmnt. with a In exception. (21;) tin-mater- utilizing the move principle m neonate-action: of the inatrmt reported by Jansen and Parr-ask (10,16). Sam infirm axpmanced eonlidsrabls difficulty in the upglic etion or m inatrumnt to titrationl (1 ’25) . Tho consensu- md to be that tho mutt-mam vaa suitable and anally mt. out of oscillation. It m reasoned that thta erratic bonnie:- m thfi vault of large immaasa 1n tm distributed capacity «minted with the coil. The Q or a parental rasonamt circuit in decraased by an Meme» 1:: diatribxztad capacity mm}: in the 3451:? may as 1"; is reduced by an max-am 1:: tbs reluctance mnaatazi into it by an increase in load. Fame, «hm: " l1. 8. patent application made. o oolution 1o placed within tho mold of o coil, the inorooaod dio- tflbntod capacity together with tho normal morocco in tho ocrioo nototonco of the circuit duo to tho conductivity of tho oolntion, could tumult in ouch bony pour dumdo upon tho oooillotor that it would cocoa to function conplctoly. Thio wound to to o logicol oxplonotion for tho difficultioa oxpoficncod by ooao snorkora in tho application or Jonaoa and Pmock'a tnotnnont. It too obumd that oll oftho instrmnto of tho coil loodcd typo had low oporottng (mountain, oonoocuontly tho calla uployod tom of tho lultitum type which hm ”wilted filth than rolotivoly high volcoo of distributed capacity. Tho dlotrtbutod capacity to in chat with tho inductance, two noun; tho coll oculvalont to o parollcl tomcat circuit having a natural rooonont tummy. Tho natural noonont from: ooto an upon limit to the Iroquoncy ot attach the coil to nodal in providing an inductive noctauoo (22). hurting o aolution of high dielectric conatont within tho coil ohould unholy otfoct tho natural tomcat froqucncy of tho coll , mo erratic behavior- conld bo axpoctod or any cactllator in touch tho porollol circuit woo o circuit olonont. In order to 11pm on instruments in this}: the oolution to ho titrotod vac ploccd uthln tho field of tho coil, com mono or prevent- in; or thinking chmo 1n diotflbutoc capacity had to to found. A! o otartlng point the inductance woo reduced to o one 1mm loop con-tract“! of 1/14 inch coppcr tubing to give it mechanical rigidity. Thio construction rodccod tho distributod capacity to o Iiniom and tho anall oocunt aoaooiatod oith tho loop no holiovod to ho diatrihutod Iainly along tho circutoronco of tho 100p. hrthor, it woo roaocnod that it tho di-otor of tho titration vooool oao ocbotantially oncllcr than tho dinootor of tho loop, tho aolution could to romeo out of tho rango of tho tiold of tho diotributod capacity of tho leap, and ohangoo in tho dioloctric conatont of tho aolntion would hm rolativoly littlo ottoct. with tho dooign or no inductanco find in thin omi- tho cporot- in: traction: of tho titriootor would fall in tho froqnoncy rango botooon 70 no. and 100 no. i baa-Ionic of tho funduontal of tho 30-2214) Iroqnoncy notor oocillotor providing a ouitoblo boat ncto in thio rong'o could not to found. For thia roaocn tho froqconcy ootor oao diocardod and tho inotrnoont ccnvortod to cno in ouch changoo in oolction coupo- oition ooro dotoctod though changoo in titrinotor cacillotor grid onrront. It tho pronioo conoorning diatributod capacity oao correct, the propcaod dooign ocnld oako tho rooponoo of tho inotrmont unduly co- pondant upon changoa in oolution conductivity, and tho motion of ooparating rooiotivo and copacitivo ccnpononta olininotod. Bonco, grid currontroadinp wold ho truoly indicativo of conductivity changes, an ohculd any chugoo in tho cporating Iroquoncy of tho oocillator. Forthor-oro, any loom o! conductivity chanson by changoo in diolootric conotant wold ho olininatod rooulting in an incroooo in oonoitivity. / / .x' 52 Tho loading on tho oscillator vac controlled by varying tho volume of oolution in tho i'iold of tho loop. With oolutiono of higher con- duotivity thia io occwpliohod by withdrawing the titration vessel vortioolly along the oxio perpendicular to the plane of the loan. Load- ing could alao ha roduood by onlorging tho diameter of the loop, which could bo onaloaouo to looooning the coupling between too tightly coupled circuito in a radio tranonittcr. It loosed that tho propoocd dcoign wold extend tho rongo of tho titrinotor to ooro practical rogiona of conductivity, with tho possibilo ity of covering tho rango of fairly concentratcd oolutiono. It woo found that tho frequency incoming inotrmont could to oaoily ccnvortod to on inotrmont of tho propoood dooigi. i ochonotio of tho inotrmont appocro in Figuro 29. Tho poocr oupply circuit io ohoon in Figuro 9. The dctoilo of the cell umbly appear in Piguno 3-9. Tho MI coll umhly woo attaohcd to tho ohaooio in tho cam pooition occupied proviouoly by tho capacity typo coll. Tho loop loada voro tominotod in banana plaza and spaced to notch tho spacing of the insulated bonono Jooko in tin side of the .ohaccio that served cl thi tor-inch to tho grid and plate of tho 955 tubo. The feedback and tun- in; capocitoro C; and C 1 were ohort lengths of finphonol RO-E/U coaxial cablo aid plugged into tho tcnclo inplmnol moptocloc mountod on tin top of tho chooaio proviouoly uocd for attaching tho 120 me. half cave lino in plooo. Thooo details on ohom in Figuroa 1h, 20, and 3.3. Alphonol RG-B/U caudal ooblo hao a minol capacity of 29.5 mfd. por toot. Thorotoro, tho length of coaxial cable uood plus the mall 53 55.2.5: mozé me; lo 536 «8.4.3.80 .3 $59“. h. - 4 a - n m - N 00H am No ”W m u ._ - - n - JJ r """" \— .VO fl lr a ._. -1. HI 80.. 7. Sb .mooq ZH ZOHBHmom ZH ammmm; 20He00 EEC» mmwmamfi; mwzlwm mQHz . Om mmDOHm amt or oopooitv associated with the ”phenol play and Jain do- torlinod tho oopooity of G; and 0.. Obviously o range of capacity vol obtoinod simply by varying tho longth of the coaxial cable ottoahcd to tho plug. 33* thio mono my ratio of O; to C, could to obtained to provido tho proper toodbwk roqnimonto on tho oitnnion dommiod. Since the total capacity in C; and C. m ontiroly hctuoon the inner and actor conductoro of tho couiol cwloood tho out-r conductor no (roundcd, C; on! C. woro ocuplotoly ohioldod {m outlido influonooo. If tho conventional typo of tuning capacitor had boon uood, otroy capacities mld oxiot botvooo tho tuning capacitor, ground, and neigh- boring objects that would vary with tamper-atom changco, vibration, and oomicnoor trotting. Thio variation in otroy capacity could be I: com-co of oocillotor inotability, and would be particularly ocricuo ot the oporoting frequoncioc of 70 no. and no". The polyothylcno di- oloctrio separating tho inner oomIcctor from tho actor conductor in tho couiol ooblo hu o dioloctrio constant of 2.29 and o you» factor of 0.000}: at all Iroqucocioo from 60 oycloo up to no no. per second, o water uboorptico of 0.005 per cent, a softening tampcrotm-o botmon 103 and 105 com Cultist-ado. Tho nochmiool nobility of tho concial ooblo io oncolloot and tho orator protectivo vim covering is non- !vgrcoccpic ood inporVicuo on oxpoouro to acids, alkali” and oil: 18). All of tho chino dooirablo proportico of tho coaxial oablo and tho rigid oomtruotion o: com-moors; brockoto, plums, oto., omtribctod greatly to tho electrical and mochmicol nobility of tho titrinotor. 56 In ordor to tocilitoto tho count-mt or chmgoo in tho grid mat of tho oscillator, o 1000 ch rooictor woo iooortod in ocrioo Iith tho grid-look resistor. tho toroioolo of tho 1000 ch- rooiotor ooro brought out to two bonono Jocko Iowtod on ono oido of tho choooio, providing o concordant and pooitivo motion to tho grid out-root notor. Tho Sorzont Hodol HI Polarogroph woo odoptcd for tho ”moot of oooillotor grid current. By hurting tho otondord 290,000 ch! 'rooiotor mppliod with tho inotrunont in cool of tho dropping norccry oloctrcdo lood gecko, tho unit pox-found oo o potootimtor. i’ho principlo io illootrotod in Hm 31. Tho loodo molly camctcd to tho dropping mar: olootrcdo ooooably pluggod in tho mood Jack of tho polu'cgrqah, voro ccnoootod to tho tominolo of tho 1000 chm rooiotcr in oorico vith tho grid-look rooiotcr. A port of tho grid bioo dooolopod by tho cocillotcr oppcoro ot tho terminals A cod B and on molly looo than 0.20 colto. With o opon voltogo or coo volt on tho polorcgroph any voltoao botvoon ooro and coo volt could bo placed ocmo tho otondord rooiotcr by on odjuotmont of tho bridge control. 11 t1: potontiol oorooo tho otondm-d rooiotor woo equal to tho bioo dmlcpod ocrooo tho 1000 cm rcoiotor no cut-root would flow in tho circuit ncdo up of tho 1000 ch: moiotor, the lcodo A and 3 mi tho otoodord rooiotor. It the bios devolopod by tho oocillotor changed, ourront wold begin to flow in tho circuit in o direction dopondcnt on whothor tho bioo no greater or loco than tho montage of tho poloro- groph upon ooltogo applied to tho otondard rooiotcr. 57 58% @2283: hzmmmao 9mm 4m manor. .1. ......... .u u _ M .1 _ + u + . . _ u . . 853m . . 9.10 000. Ir. “ 83245 _ u _ _ .. u - u .4 V _ n 4 r llllllllll L v Tho ocolo of tho current mum-in; actor of tho polu-opoph lo 280 on. in lonzth. booty voluoo of etc-root naming oonodtivity ranging from 0.003 niomapo por III. to 1.500 Iicmnpo. per 3. con ho oolcotod by com of o twnty pcoition “itch. “to: portoning o for oxplorotory titrotiono o “nativity could ho ooloctod vith which tho want-chant“ oncoontorod in tho corona of o titrotion cororod tho ontit-o 280 III. length of tho room-du- ooolo. Sonoitivity mono wot-o obtained for tho titrilotor by tho om proooduro provioooly uood in concoction with tho frequency honouring intro-out. Tho omoo oppon- in Figures 32 and 33 and tho cornopond- 1ng inotmont odjmtmnto oppoor in Tohlo II. In obtoining tho curvoo two loopo of dirrmnt dimotoro mo uployod. You-icon co-hinotiono ct c; md C. and voml poodtion won doc coed. is. ohcon in Figure 31;, «cool position coo indiootoo o and” voluo ‘of. ”lotion woo Iithin tho rum or tho loop. In mool pcoition to», 1'1er .35, o onollor volt-o or oclotion no in tho field of tholcOpdnco tho mool had boonuithdromhyon motoqncl to tho width of tho ring that had been inocrtcd hotooon the lip of the vocal ond t1! ring ottochod to tho oportoro in tho top of tho shield modal: of tho coll. A point of intcroot in concoction with tho oomo in that in order to roach tho non concentrated rang", tho loop dimtor woo incrouod, rooultioz in o louorod oporcting frequency. In all tin-Motor. proviooo- ly "ported, in order to oxtond thoir rongo ct ”nativity to rogiono 59 I4 I2 IO 28 24 20 6 ozadwm 2 1952024)de MOLARITY NACL WIDE RANGE TITRIMETER SENSITIVITY CURVES . FIGURE 32 . GALVANOMETER READING 28 24 20 0.: 2 LC MOLARITY ' NAOL .FIGURE 33. WIDE RANGE TlTRIMETER SENSITIVITY CURVES. .occaaoaooc oggughofiaz. $13339 £1.23; o m.n. « Hothoia: .Eoeu 3 38.5". 88»: 53%...mm 238.30 2.3- on as. 3 :8 8.3m 8 .83 at: . .5oi5.§~€.8o88&83§t 5 H83» «5.53 to a 8533 Hot! on .mn to an 225 3 zoom .8328 H8...» .2; has Lounge 31: m .5 3 n .3 .3. a .8 HH « .8 OH H .8 0H H RH than 88 “3.13 93 2. «H93 H338 .3 533 83890 o QR 0.? H «m H H a 3:3 4.3 8.0 a «a H H H. «H huH 3.0 n a H H w HH «AH mdo m «a H H a 9.. 0;: “Ha H mm H H a a E. cod « .a u a m e E 8.0 . H .8 H m m 2. «.2. 3.0 H a u . a m 0 3. 09¢ H R u m n m W... 8.0 H 8. a n N a a.» 3.0 H 9 w m u H m.» 3.0 u 8 u H a N m.» 3.0 H 3 a. H a H 3:.- .p H «a 5 mm...) icooHaH-E div 1&3 no no only: «553 63.5 «.528... H38» 5&5 cottage gm 2. Bun—«Ba mggo Egg our: man: H San 'Jo. '4- . 'A -o :‘h -‘ “-JHM.~‘.9. .' .. -‘. FIGURE 31;, VESSEL POSITION ONE. 5 To a If r! O . "do- . ‘ ‘ .Q‘ . FIGURE 35, VESSEL POSITION TWO, 63 of higher conductivity, tho Operating Iroquoncy or the oscillator had to bo inoroocod (1,2,3,6,7,8,19). Em though Bloodol ond Holmtodt (3) mo ohlc to reach o tnqucnoy of 350 no” tho instrument ohawd no oomitivity with oclution concoctrotimzo greater than 0.3 cooler in tom or sodium chlcrido or 0.1 who in tom of lqdrootaoric acid. Tho Inc authors (3) won dalo to vary tho loading on their oooillotor by odjuotuont of vooool pooiticn in tho cud of tho concentric lino uployod ot tho obovo morocco: , but only tho unoitivity of tho instru- nont to chmgoo in oolution cmpcoition no reduced. Tho odyzotocnt did not chift tho region of am ”nativity for higher concentra- tion. of oodiu ohlcrido or hydrochloric ooid. Withdrawing tho. vooool in tho mount inotmont lowers tho oonoitivity of tho inotrooont ocnouhot, but at tho sumo tino oxtondo tho rcngo of tho inotrunont to higher conductivity rogiono. Thuo it oppooro that in tho proocnt inotrnacnt, cporating Iroqucnoy'in of littlo significance and any' rofion of conductivity may be roaohod by varying loop dimotor, vooool polition, or tocdbook. ‘Tho operating {cocooncy-cf tho oscillator is tho Iroqooncy nomad by tho oocinotor with tho portionlor dimmoion loop and tuning capacity ocloctod in order to work in o opacifio range of conductivity. Tho ocnbinationo of loop, vooocl position and foodhock capacity and in obtaining tho oonoitivity mo by no means cadmuot tho possibilitioo. Intorncdicto curvoo could ho obtained with intermcdioto value: or cell paranotcro. 6h Cum 12am oourvotnro uhiohougguto um opointotin- {lootion bod boon reached, but tho curvaturo io bolimd to bo duo to tho manner in fidch tho dot: for tho pointo on tho our" vor- ob- toinod. Inotood or adding olootrolyto to tho blution in tho ”ml, tho voml woo tint filled with 5 molar oodim chloride oolution and damn“: votor added in mum-ed portions until the oolution m t ‘ mm. n this point tho mool m filled to oopooity. rho mool m mud ottor recording tho initial and final recorder ”dingo and o portion of tho oolution moved permitting has-tim- dilution. the original pooition of tho mool in tho coll woo-bl, no not portootly produoiblo. his mid ooommt for the mature chromed. Al indiootad in stlo II, m of the our!" van tor-mow at tho point of mcuh d-pod oooillstiono which was duo to moo-ire loading. 30! tho ohopo of o titration curve io affected by tho oomontro- tion at which tho titration is carried out nay bo predict“! Iran the sensitivity cm and boo boon odoquately diooulood by othoro (2,3,h,7,19). Tho um. range titrimtor is unique inooter oo theoretic- all: on infinito amber of mitivity our": «1 «:11:le through odjuohonto of vessel pooition, loop diameter, longtho or 0,, and 8., and ratio or C; to c., on that omeuivo curvaturo 01' rover-o1 or titra- tion curve: a different oomntretiono of sample and titrant m mod on bo eliminated by o proper odduotuont of the titrinotar. Tho voltago improoood oorooo tin 1032:) am resistor in caries with tho grid-look moiotor by tho polorogmph places :1 mall want of find bio. on the ancillator. Tho offset of varying acmmta of find bias on tho oonoitivity our-vol io ohm in Figure 36. in increased bio. roduooo tho lhopo of the unoitivity .m olightly. Tho effect ohm: in Figaro )6 resulted from a 100 par cent increase in 13130., Ordinarily, variation in fixod him on load than 10' per cent. Than-ohm, it my be assumed that comments of tho bridge control on tho pclarogroph horo a negligiblo effect on acnaitivity coma. Tho inotmnt rammed to changes in liquid lava). aa ohmic by Figaro 37. Dita for tho onrvo Ivoro obtained by adding nomad incro- Ionto of 0.25 molar oodiua m to on initial oclmo or 90 ll. of 0.25 molar oodiul chloride. when tho liquid lml io abovo tho gromzdod band in tho top of tho coll ohiold aooanbly, tho inotmnt no 1m:- roopocda to changoo in liquid lml. Tho ottocto of changoa in liquid level and dilution voro chum by adding diotillod motor in nomad incremento to 75 ll. of 0.25 nolcr oodim ohlorido. Tho ottocto wore found to oppose one: another which oooonnta tortbonaamintheoumofriguro 38. i.- Hodii‘icoticn of the Wide Ensign Titrimtcr Tho 120 no. lino cnplcyod with the frequency mmring inotmcnt vol mbotitutod in the piano at C; and C. and the magnitude of the grid biao indicated that the oscillator an oscillating vigomaly with 0-,, 11mm in Figure 29, in tho circuit. Tho oonoitivity mo of Figumc 39 and LO wars obtained utilizing this 120 m. 11:19 and a line READING GALVANOMETER 26 24 (A) 22 2O (B) (A) BIAS = 0.2 VOLTS J J J I I I I (a) BIAS = ofivous I 0.0l O. I MOLARITY NAGL FIGURE 36. EFFECT OF FIXED BIAS ON SENSITIVITY CURVES. GALVANOMETER READING GALVANOMETER READING 6'? :2 r . l . no . I I I LEVEL AT BOTTOM OF moan BAND 3 s 4. 2 o I00 I20 I40 I60 ISO ML. 0.25 N NACL FIGURE 37. RESPONSE OF WIDE RANGE TITRIMETER TO CHANGES IN LIQUID LEVEL. '8 I I I I6 I I AT BOTTOM OF I4 I2 I0 8 6 4 95 I35 I75 2I5 TOTAL VOLUME (ML) 20 60 I00 I40 ML. H20 ADDED FIGURE 38. RESPONSE OF WIDE RANGE TITRIMETER TO CHANGES IN LIQUID LEVEL AND DILUTION. READING GALVANOMETER 68 28 ‘Il Ill (3) 24 I0 20 9 I6 8 l2 7 a I. 4 5 0 4 0.00I 0.0l 0.| FIGURE 39. MOLARITY NACL SENSITIVITY CURVES OF MODIFIED WIDE RANGE TITRIMETER . GALVANOMETER READING 69 20 5 v3 FIGURE 40 . MOLARITY NACL SENSITIVITY CURVES OF RANGE TITRIMETER. MODIFIED WIDE opprozhotoly coo-third longer. Tho moitivity oumo oro oinilor to thooo obtained with tho lid! raga inotnnont and tho doto pox-tain- ing to tho mo oro givon in toblo III. Tho oodo of oooillotion m not dotinitol: ootobliohod, but it io bolimd that it io oioilor to tho node of oooillation in o ring oooillotor, which ouggooto thot o titruotor oay poooibly be omtructod coins o conventionol ring oscillator. The troquoncy of tho oooillotoo- no nonitorod oo olootrolyto no oddod to diotillod rotor in tho mool on! tho operating £212qu of tho oscillator inorooood oith incl-oiling conductivity. In all otlm- titrinotoro, including tho uldo rango titrinotor provionoly dioouoood, tho froqoonoy doorooood Iith inoroooing conductivity. Titration! with Promos; HomdnLInots-tmoo} m olootronio apparatus m toned tip for two houro before use. i. ”mired volxmo of omplo to bo’ titrated m tronofomd to tho woool on! diluted to o unison: total volmo or 100 ll. nth o mum-ed voluuo or W voter. The vooool no inoortod in tho tiold of tho plat”, o notor Moon poddlo otirror introdmod md tho oolution otirrod for too oimatoo to ottoin taper-om equilibrium. tho truancy note: oooillotor woo odjuotad to ooro boot nth tho inotrmnt oscillator. . Tho dial reading of tho Iroquonoy not" on ”corded. Imromnto of reagent If. added from o 50 I1. or 10 ll. bunt, on the oitnotion roa- quirod, and tho fmooncy motor mtorod to sou-o boot otter ouch 2.5.31.3 III IMSI'ML‘HTB w mama-.23 mm mm; 'rmmmm Panama: 'ro smmvm cumzs Cm . " Frequency Semi tivity 51'1de Von sol , umber Loop Lino “I? (80.) (In/nu.) (3 81pm) Position“ 5 1 1 91 0.15 11.2 1 6 1 1 91 0.13; 17.0 um“ I. 1 2 103 0.15 10.8 1 3 2 1 95 0.15 10.8 1 2 2 2 1:38 0.06 8.8 2 l 2 2 108 0.56 8.8 l * Rotor to Toblo II n Lino 1 117.5 on. 368/0 Coaxial Cable Line 2 85 .0 on. ESE/D Coaxial Cahlo m Rotor to Table II a“! Vooool roiood 3 ca. 72 ioormnt had boon added. Tho titration on curried beyond tho equin- volonoo point. Tho frequency Iotor dial rudingo varo plottod ogoinot ll. of roogont oddod. Cmoo ooro arm though tho poioto. Tho oqoivolonoo point no road at tho point vhoro too ourwoo interacted. Prolininory qualitativo titration of Widow ooid and oultnrioocidoithoodiutvdmoidoooroorriodoottoteotiootmont porter-moo at 12 .2 no. la otondord oolution or phoophorio ooid m then umm no: oodim hydroxido a om- mqmmy. Other noutraliootion mootiono voro oorriod out at 38.8, 6'), and 120 I0. Tho nonlto on liotod in Table IV Ind VI. A oorioo of precipitation reaction! wore oorriod out ot 120 m. Tho rooulto ore liotod in Toblo 7 and VII. Titratim with tho 31(31me Iitrinotor Tho titrhotor oscillator and polorogmph A. C. circuit mo nomad up for too hours, or loom. i momma worm of omplo woo promrod for titration by dilution with o momma volume or diotillod vote:- to I o ninimn um). volun- or 150 .1. Tho titrotion voml m loomed into tho 23.01:! of tho 100p and film“ made to tho mm‘omo accord- ingto tho W ginnholov. After thooo odjuotaonto hodhoon m. o lot-or ctr-inn glue paddle otirror was installed in position, Woto or titront who oil-rind, recorder ooodingo: token, and tho al. of titrant added plotted ogoinot moron roodingo. Como mo dram through tho pointo and the oquivolonoo point mod ot the iota-notion of tho mo. 73 An muotrotlon of fin wrong-smut of tho march» 11 31mm in riguro hl. Tho animator ooo connected to tho no volt A. 6. power lino through o Solo oomtont voltage: tranorom to aim. flue tun- titans in 11.30 Voltogo, Emcodum fogjhe PM? MW of tho Wig-13 3&9 Tim”:- The 7.5 on. loop and the 10 on. lengths 01' c. at! c. m 12111;;de into their ”spout-11‘s positions in the tux-hater. Tho «lactos- switch of tho Boothkit vacuum tube voltnetor in W to tho D. G. minus pooition, and the tango switch to tho throo volt male. Tho common loud or the voltuotor is connected to tho om'eoolo of tho fitriootor ad the D.O.loodoomotodtothop1dortho955tuho. Ap-oundloodlo commuted rm tho ohmio or the titflmtor to tho ouo pound ooh- motion oood for tho polorogroph external ground ploolna tho ohooaio of both me at tho one potential. It thio to not dono, erratic oporotion of tho recorder romlto. ‘fho D. X. 3. load. Ron tho polorogroph on enacted to tho color coded honouo amino on one Mo of. tho “We! ohouio. Tho pooitho n. a. 1:. load 1: motod to tho rod Jock at tho nozotivo lood to tho block jock. With thio carnation at tho D. H. E. loodo, tho D, K. 2:, witch 1o outohod to the minus position. Ho duping of tho yolwo- gray}; circuit to used, 1.0., duping witch turnod off. Boron the “tool 1o lowered into the field of tho loop, tho grid his: indioomd on tho vammm tube wlmtor ohould be Wkly 734 .mZOHBM‘mEHB mom mp Hum magm.,\._$q 9,~H.\H00mmflu 92¢ .mnfi\mwom}} "f-j‘l‘h‘i‘ . L 51‘s 1-: a ”bywaiJ: EVL‘XJL t3? r?‘( 'Laggq' E;.§:.flu “air: '1‘” m {J mu 3301‘5591. 3'15! MM“ m 12.51%. 0.. 00““:‘3‘.~‘*.».43mn range 1155 mt. b5-xisn 55522-551. T125 2155 of a 15532:? lamp, 15:33::- 1515:1115; of C 1 53:1 8, 5:11 15:72.52- cell ”5'5“” ““1 “m3 3 t! a 5:31.59... 811-3322 5.25:5: in which Max:255 15 55111 Wit $151.? ‘3 53.31% , R x 5-. D If p- u‘ .. kl 17:55:36) hJIfiE‘ 3 1.753 3""???‘73‘7‘ ""-‘ 117' v'J-‘r-wv‘ 1...“? a) In 23"."1421275 111' _ 7, t3; =5 (“TH-1:7 ma.:3..;rinzg; 1:57:253'22555513 a 511-51: 5 5nd r5151: 92:13; 53. .1:.2': Cl... . 15:3. 02":11“ -5503.“ m5 c0755”: '54:}. 55 wall 53 a. practi- cal t5.t.“5:.."’.