University of the Pacific University of the Pacific

Scholarly Commons Scholarly Commons

University of the Pacific Theses and Dissertations Graduate School

1957

A 120 megacycle self-contained high-frequency titrimeter A 120 megacycle self-contained high-frequency titrimeter

John Kyle Clinkscales Jr. University of the Pacific

Follow this and additional works at: https://scholarlycommons.pacific.edu/uop_etds

Part of the Chemistry Commons

Recommended Citation Recommended Citation Clinkscales, John Kyle Jr.. (1957). A 120 megacycle self-contained high-frequency titrimeter. University of the Pacific, Thesis. https://scholarlycommons.pacific.edu/uop_etds/1346

This Thesis is brought to you for free and open access by the Graduate School at Scholarly Commons. It has been accepted for inclusion in University of the Pacific Theses and Dissertations by an authorized administrator of Scholarly Commons. For more information, please contact mgibney@pacific.edu.

A 120 MEGACYCLE .. SELF-CONTAINED HIGH-FREQUENCY TITRIMETER

A 'l'hesis

Presented to

the Faaulty of the Department~ or Chemistry

Oollege of the Peaifio

In Partial Fulfillment •• of the Requirements for the Degree

Master of Soienoe

By

John Kyle Clinkscales Jr • . . . June 1957

iii

ACKNOWLEDGEMENT

Appreciation ia expressed to the faculty members of

the Chemiet~y Department of the College of the Pacific and

especially to Dr. Herschel Frye for the guidance and cr1t1-

oism given to the writer during this period of study.

A 120 MEGACYCLE

S~LF-CONTAINED HIGH-FREQUENCY TITRI METER

FORWARD

The analytical ohemist is ever eager to 1mp.rove and

expedite present analytical methods.. In the past ten years

considerable interest .has been elicited in the :t'ield ot high

frequency oscillators and their application to analytica l

chemistry. One of the main reasons for this interest is the

un-iquene-ss- ot--t-h:e-- appa-ratus-. - No- El-irect-e-ent aa-t - ia mad-e

between the measuring instrument and the solution. Credit

tor this interest must be given primarily to Jensen and

Parrack of Texas A & M University. Their artiole in 1946

described a simple tuned plate-tuned grid electronic

oscillator, operating in the high frequency range. A

solution w~a exposed to t he electromagnetic field or t he

plate ooil. During tne titration the electrical character­

istics of the solution changed . These changes were retleetm

in measurements of the electrical constants of the osoUUator.

Upon analysis tho constants clearly showed the end point and

yet no physical oontaot had been made with t he solution.

Sinoe the instrument ot Jensen and Parraok many mod1fioa­

t1ona have appeared and even entirely new instruments.

However they s till keep the one common feature: no oontact

with the solution. In addition to titrations, the instru­

ment has been used to advantage in many other fields of

analytical chemistry . After ten years it has clearly

established itself as a valuable tool rather than just a

l aboratory curiosity.

vi

The objeot of this present research was to build an

original instrument and teat its etteotiveness in as many

fields as possible .

TABLJ~ OF COl'l'l'KNTB

A Description of thu Instrument • • • • • • • • • • • • l

lexpertm.en tal Procedure. • • • • • • • • • • • • • • • •

Theorot1oal Gona1derat1one tor High-Frequency Osoillators • • • • • • • • • • • • • • • • • • • • • •

Ohemioel Ana lysis w1 th tbe Uigh•»'requeaoy Oao11lator •••••••• ••••••••• • • • • • •

(a) H1nnry Mixtu1·es . • • • • •

(b) ~1trat1ons •••• • • ••

• • • • • • • • •

• • • • • • • • • (o) Complexes •••

(dl__Reaction Rates.

• • • • • • • •

• e • • • • • • ------(e) Ohromatogr~pby, • • • . ~ . " .

• • • • • •

• • • • • •

.. . • • • •

5uniP18ry • • • • • • . . ~ . , . . . . . . . . " . . . . /\ppendix • • • 0 • • • • • • • • • • • • • • • • • • •

Li tero tu..re c 1t od.. • 0 • • • • • • • • • • • • • • • • •

7

10

r1

17

20

26

27

27

29

)0

52

l

5

6

LIB'r OD' FlGURKS

OllAPHS

'fltrutiun ... Uod1um Hy<lrQX1dt1t ~•nd Hydroohlo~io ;~ oid • • • • • • • • t • II II t • • )0

Titration - Sodium Hydroxld~ and Aoetio f,oJ.4. • • • • • • • • • • • • • • • • • • • • • )l

't'1tret1on - f3od1wn Uyaroxi<Je una 0Jte l1o Aold ~ • • • • • • • • • • • • • • • • • • • • • J2

'£1 tratlon - Bodium liydro:d.tle an.o Ph.osphorio Aoid lUe h•l'tequonoy Method • • • • • ))

Titration ... s odium Uydroxtde e.nd l~hoa ht,rlo J~ c1cl Potf.mtiomotrio Method , • • • • 34 ----

• • . ))

'I '£1trat1on • !J1lver Hltra to and Sodium Onloriao. • • • • • • • • • • • , • • ~ • • • • 36

S 131.n4$X'Y M1x.ture - a*'n~ene end UitrobGnzen& • • • )7

9 Blnary Mi~turo - Water ~na Aoetono ?Jatur and ;-:tllyl ~\loohol ifat6r and liiOXetne., • • • • • • )8

10 ~1nary Mixture • Water and Aoetlo Ao14 rlatur artd Propionic Ao1d • • • )9

. ll

12

l)

6te b1l1 ty ot I IU) tl'\.UilOnt , • • • • • • • ., • •

DCRi\loJA ~i'lC lllAGHAMG

Oso11lator • Olo.pp. • • • • • • • • • • • • • osoillctor - Oolpitta •••••••• • • • •

• 1.2

• 40

• 40

Figul'e

14

15

16

17

LICJT OF F::tCHJlU:S

Oscilla tor • Crystal. • • •

Oaoilletor • Hartley ••••

• • • • • • • •

Page

•• 41

• • • • • • • • •• 41

Osoilla tor .. 'tuned r)lete•Tl.Uled Gr id • • • • • • 42

Instrument .... Less Power l)upply. • • • • • • • • 43

18 Power Supply ••••• • •••. •.••. .•• 44

Parts Lis t t or Above Sohematlos ••••• 45

PHOTOQRAJ?US

g__~t end Power su

20 Instrument - Baok view.

• 0 • • • • • • • • 46

• • • • • • • • • • • • 49

21

22

I nstrument .... ·rop view , • • • • • • •

Call Holder - Bottom Removed. • • • •

• • • • • 50

• • • • • 51

A DESCRIPTION OF THE INSTRUMENT

This is a heterodyne type of instrument . There are

two separate oscillators mechanically shielded from each

o~her and electrically isolated by the two identical butter

stages. The working oscillator has its frequency determin­

ed. by the solution that is placed in the spacial container.

The reference oscillator; however , is controlled by two con­

densers in parallel. This givea it a large tuning range and

enables th~ operator to find t he frequenoy of the wo~king

oscillator with rapidity and ease. As the t wo oscillators

approach the same frequency a heterodyne or beat frequency

will be heard ~ When the oscillators are tuned to exactly

t he same frequency a zero-beat or null is heard . The but ...

fers are R ... o ciroul.ts designed to isolate the oscillators

from eaoh otheri The mixer, deteoto.r and audio stages are

stan<la.rd design. The earphones oould have been repa.aced by

an additional audio stage and a loud-speaker, but it was

considered a luxury and not necessary•

Oonstruotion of this unit is relatively simple, The

most important consideration is the trequenoy stability,

Ideally the chassis should have been constructed from cadmium

plated steel. Aluminum was chosen instead beoauae ot the

ease ot construction. The id&a of this instrument is not

original. Actually this a oomb1nat1on or two separate and

original instruments. But a literature sear ch reveals this

2

is the first time any one has ever oombined both in this

taahion. west, Burkhalter, and Broussard (19,0) built a

similiar instrument using a Clapp type oscillator in the low

frequency range. Johnson and .Timniok (1956) built a single

120 megaoyole oscillator and follow~d the reactions with a

Sargent Model XXI Polarograph to measure the grid current,

or observed the frequency shift with a BC-221 frequenoy . meter. The present instrument re~laoes the Clapp osoillatom

with the 120 megacycle halt-wave oscillators. The result is

a stable, easily operatea instrument. The auooess ot this

instrument depends on several faotors . Both oscillators

- have- a oommon- pla-te- and 1-1-lamen-t supply· ny: hif-t - 1n.----

frequency because of power su~ply fluctuation will there­

fore oauae a similiar shift in both oscillators. Since we

are measuring the difference between the oscillators at all .

times, e~en though a shift takes place, the difference or

beat frequency remains a oonstant4 The use of a miniature

955 tube and RG8/ U flexible coaxial oable make a very simple

and stable arrangement at this high frequency~ The RG8/U

cables are supported by a wooden trame for meo.hanioal

stability •

The titration vessel is pim111ar to the one used by

Johnson and Timnick . It is attached to the chassis by three

banana plugs. The plastic soluti9n container is held firmly

in place ·bY plastic rings a.nd is mechanically stable. 'fhis

J

is important since any movement . of the container causes the

frequency to shift . Although the plastic cup is firmly held

it is easily slipped out for cleaning after each experiment.

The container has a total capacity ot 200 rol. It is a

plastic bottle 2 inches in diameter and 6 inches long, The ~

two oscillator electrodes are sil~er plated strips of metal

about J/4" x 2" and are curved slightly to fit around the

plastio cup. Above the electrodes is a 1/2" piece of

aluminum with a 2 1/6" hole drilled in it to, aot as a g;round

ring. This ground ring is a very important part of tha

apparatus . It liquid is slowly added to the empty oup the

~equenoY-shif~s~and-~n b~llow~ ~ith-Lha ~ab~------+-­

referenoe oscillator. With the ground ring in pla ce the

shit t takes place only up to a bout 80 ml . .Attar this the

frequency remains a constant . By starting every experiment

with a minimum of 100 ml . of liquid in the vessel, any

change that takes place is due to . a shift in the solution

composition and not just a result of physical capacitance.

As was previously stated, the reteronoe oscillator

has two tuning condensers in parallel. The black knob on

the side of the reference oscillator controls the l arge con•

denser that is used to find the heterodyne. The ema~l

condenser is controlled trom the front of the instrument by

a National precision dial with a 1000:1 ratio . After the

heterodyne is located by the large Qondenaer the reaction is ]

then followed by moving the small condenser until a zero­

beat is heard, and taking readings from the National dial,

The power supply is of conventional design~ The only

requirement is that it be constructed of quality components

that are slightly over-rated for cool, efficient oper~tion.

The power supply shown in the accompanying photographs 1s

much more oomplic~ted than is necessary. It is an experi­

mental model that was already on hand ond was used to save

time and 1noney.

Anyone with previous experience in electronics

should have no difficulty in duplicating this instrument.

Plaoe~ at p~ is not critical In the _oscillator

leads should be kept short and mechanically stable . NUIJ:lber

12 tinned copper wire was used in both oscillators to in-

crease mechanical stability . The 9S5 oscillator tube -1

sockets are ooram1o to minimize loss a t the high frequency

and are mountecl on rubber grommets to reduce meahanioal

vibration, The l ength of the RG8/U coaxial cable ia 90 o~.

for a fraquenQy or 120 mo. Shorter lengths were tried in

an effort to raise the troquenoy, but the resulting instru­

ment showed signa of instability and it was necessary to

return to the 90 om. length. The length of RGS/U on the

referenoe oscillator is several om. shorter than this

however. The additional oapaoitanoy of the paralle~ oon-•

denaers compensates for this and keeps the tuning range

within 120 mo. The working oscillator is anolosed in a

2x3x6 inoh box underneath the chassis" Connections to the

titration oell are mada through the rear ot the chassis by

5

l three large, silver-plated banana plugs. The referenoe

oscillator is in a 5x5x6 inch box on top of the oha~sis.

The National dial is mounted on the front panel and is con-

nected to the smallest of the two frequency determining

condensers. On the side of the box is a knob directly oon­

neoted to the large frequency determining condenser.

Both oscillators have their plate voltage stabilized- /

by a voltage regulating tube (OA2). The output of both

ao ilJ..a to.-r-a-i s-c-Oaple d th-~oug-h-v er-y-small-oe-rami c c-ond-en-se ra

and coaxial oables to the grids ot the buffer stages (6SK7).

Eaoh of these tubas is a ·.low ga in R•C coupled sta.ge designed

to isolate the oscillators from each other and prevent pull­

ing as the oscillators approaoh the same frequency. The

output of both buffers feeds into a 6L7 mixer./ Rare the two

frequencies heterodyne or beat together . There will be an

addition signal and a ditferenoe signal. Only the difter~

enoe signal will be in the audio range and is passed on to

the deteotor (6H6 ) for reot1fioation. This small audio

signal is then amplified through two 6SJ7 type pentode

amplifiers, and the tinal output is fed into a pair of

earphones. Each 6SJ7 grid is controlled by a separate gain

control. The first oontrol is on top of the ohassis and is

adjusted by a sorewdriver. This is adjusted for optimum pe~

)

6

formanoe without ovardr1v1.ng the tube . The second oontrol I

is on the tront panel and is adjusted as needed .

7

EXPE!RIMENT.AL PROCEDURE

In all experiments, . the following procedure was used.

The power supply was turned on at least 45 minutes before a

run was to be made . This eliminated drift and stablized the

instrument. The pla s tic container wae pushed into tho oell

holder and the holder was chocked to be sure it was firmly

attached to the chassis. The solution to be analyzed was

then added to the cup (100 ml. is the minimum allowed at the

beginning). The stirring rod was attached to the stirrer

and adjusted no deeper than chassis level in the oup. The

filled buret was then brought into place and the tip put

into the oup . The ~tirrer motor was turned on and speed

kept slow. The National dial was adjusted to about 120 and

the large knob on the aida turned until a aignal was heard .

The earphones incidently were not worn. They were left open

on the talbe and the volume control adjusted to about two- (_{:)

thirds of full volume 1. The signal was e~sily heard under

these oonditio1un After the signal was detected by adjust ..

ing the knob on the side of the instrument, then the

National dial on the front panel was adjusted until a zero-

beat resulted. A known quantity ot liquid was added from

the buret to the solution in the cup and again the National

dial was adjusted until a zero-beat was heard . This pro-

cedure was followed until the end- point ~peared passed .

The data sheet now oontain~d two columna: one indicated the

volume or liquid added and the other the dial reading tor

8

e a oh suooeesive addition of liquid.. The data were then

plotted on standard graph pa.per as dial reading (ohange in

frequency) vers us volwne of liquid a dded.. An interpretation

of these our Yes will be given later.. The procedure for the

binary mixtures we~e a l ittle different. It was not possi­

ble to remove the oup during an experiment because the

t.requenoy would be shifted sligbtly. All the solutions tot"

the experiment were prepa red and just 100 ml. of eaoh· was

taken . Tbe first solution was plaoed in the oup and the

dial adjusted to about 230. As before the coarse adjus t­

ment was made by the knob on the side and adjustment to zer~

-----b-e-a-t-a-nd-the- wh:o--l-e-p-roo-ed-ur-e- o"t-empty-1-n-g-a-nd-fi-l-i t-ng-wa-s------­

repeated. A oh.eok was made by making the last solution for

the experiment the same composition as the first . If the

dial reading was not the same as the original setting then

the whole experiment was discarded. Agreement in almost all

oa ses was excellent.

The National dial is a precision dial that oan be

read to three plaoes directly and the fourth place estima te~

In the judgement of the writer it oan be estimated to ±0.05.

When the dial is exactly adjusted to a zero-beat the dial om

be moved about +0.05 without affecting the signal. This -represents a precision of 0.2% for the average titrational

10 dial units . over all this apparatus is stable, but oare must be

taken not to move or jar the equipment onoe an experiment is

9

under way . Care should also be taken in stirring the

solution. If it wer e stirred too rapidly, a oone of air

would be drawn into the oup and greatly affect the readings.

10

THEORETICAL CONSIDERATIONS It'OR HIGH FREQ,UENOY OSCILLA'rORS

Instruments are divided into two classes. depend~ng

on their mode of coupling the sample to the instrumental

circuit. If the sample is exposed to the eleC'troatatio J field of the condenser, it is s~id to be oapaoitively

coupled; if it is placed in the plate coil; then inductively

coupled. _Either method of coupling depends on the

dielectric constant, speoiflo oonduotanoe, or both (depend­

ing on the speoifio circuitry)• The indication from such a

ohange i$ dependent to a greater or lesser extent upon the

eleotronio circuitry. The capacitive efteot can be predict-

ed with a high degree of aoouraoy from theoretical con·

siderationa, bu~ the inductive effect is very complex and

cannot be predicted with aocuraoy •. While the inductive

effect has been studied in great detail for speoit1o instru­

ments most of the theoretical work haa concerned the

oapao i tive type. In the aotual instruments measurement of

grid current, plate current, frequency shift, oapaoity

ohange, etc. are .all used as an indication o~ the changes

that are tak'ing plaoe in the solution, In add! t1on to the

methods utilizing the direct effeots of the solution on

tuned oirotiits and oscillators, additional methods for high

frequency titration have been desorihed. Hall and Gibson

(1951) used a twin•T impedance•measur1ng circuit to study

ohangea in solutions.

A review of circuits in use in high frequency

instruments would most likel y include one of the following

basic oscillators .

ll

Qlap~ osoillator-(Fig 12} characterized by its extreme

stability, and exoollent ohoioe for this type of instru­

ment . The oirouit owes its stability to relatively large

oapaoitanoes in parallel with the tuba oapaoitanoes. Varia­

tion or the latter due to vibration of thermal expansion

have only a slight effect on the frequencr . No investigator

has been successful with this olrouit above 30 megaoyolas•

however.

- Ha-rtl-ey oscrilla-t-or-tFig. 15 )-one of t-he- si-m-p-len-t aelf•e-xo 1 ted

oscillators . Its distinguishing feature is the tapped coil

that is used to obtain the feedback necessary for

oscillation ..

Colpitts oaoill~tor- ( Fi& 13) obtains the feedback necessary

to support oscillation by dividing the tuned oirouit into

two parts.. This d iv1s1on is accomplished by means of a

capacitative voltage divider made up of o1 and o2 in series

sbunted aorosa the coil L, It will be noticed that the

principle involved is the s~me as that used in the Hartley

oirouit except that it is tne · oapaoity which is tapped in­

stead of the ooil~

Tuned plate~tuned f~~ osail lator- (F1g. 16) proper tuning

requires two controls unless a gang condenser is used. Its

principle advantage is the great tlexi~illty of tuning.

Because both plate and grid circuits oan be tuned; optimum

feedback and frequency conditions c~n be obtained, with

r esult ant gain in output stability.

12

Cryat~ oscillator~(Fig . 14) tho circuit is fundamentally a

tuned plate•tuned grid oscillator, except that a crys ta l is

used ~a tna grid tuned circuit~ Posit ive feedback i s pro­

vided by the grid to plate capacity of the tuba~ Th~

orystal oscillator is sueful beoa uso of ita simplicity, the

fact that the components naoasuary are not as critical as

those found in more elaborate types of cryst al oscillators .

The tuned plate-tuned gr id oscillator 'of figure {16)

has t wo t-un-e-d-oncui ts -whio h---mua-t be a-d-j-u-ste-d-to-resonate at

approx1mato1y the l:iame frequen¢y for oscillation to take

place ·. In order to use this dev 1.oe to follow a ti tra t1 on ,

the cell is placed in the pl ate c ircuit and then the plate

and grid condensex·s are resonated to bring the oircui t into

oscillation. As the titration proceeds the resonance of the

plate circuit will change~ The amplituda of radio~trequenoy

oscillation will be red uced and there will be corresponding

changes in the plate· and gtid ourrenta and voltages~ Such a

device oan be made very sensitive and many investigators ba~

done excellent work ~tth them. One of ~he disadvantages,

however, is that the adj ustment may be orttiQal and it may

be difficult to achieve sufficient range and stability for

some work• The crystal oscillator of figure (14) is similar

to the tuned plate•tuned grid osci1lator, except that a

13

quartz crystal between meta l plates replaces the tuned gtid

circuit. It has two advantages over the othe~ oscillator

circuits. It may be readjusted to the same resonant

frequency as the loading is o.banged, and as the value of c

is deoDeased. the point at which oscillation starts ~s

abrupt and oan be reproduced very exactly. If a oell were

placed in parallel with the tuned plate circuit. C would

have to be readjusted to compensate for any changes that

took place in the solution. As 0 is varied so will the grid

bias voltage change, A graph ot maximum grid bias voltage

versus 0 then would be a goo4 indication of the change$

-------'t-&~1-ng-p--l.aG-e-!-a-t-h-e-a-el-u-t-1-0-a-.--tPhe---G-e-l-p!..t-t-a-e-1~I1G-u-1-t-e,r---------­

!'igure (13) has only a single tuned oirouit tor both plate

and ~reid oirouits of the tube• Honoe, capacitive c~anges

across the terminals ot the induotanoe co.tl of this oirouit

w11r shift the trequenoy; but will not oauea the plate

oirouit to detune with respect to the grid o1rou1t. If two

suoh identical oscillators we)Je used and only one loaded

with a solution, the other could be used as a reterenoe

oscillator and beat against the other for deteotion of any

frequency shift. 'rhis is· the prJ,noipal that is used in the

writer's 1n~tl'ument;. I.n instrwnents that have be$n describ-

ed at low frequency. this change in frequency is very sligh\ .,

usually only a few hundred cycles ror a given increment of ·

titrav.t . The usual method of detecting a ohauge aa small as '

this is first to tune the two oscillators to a beat frequency

14

ot say 5000 oyoles per seoond, using a frequency mater or

a udio oscillator ~nd osoilloaoope as a standard. After the

increment of titrant is added to the oell the beat frequency

shifts to a new va lue and the new trequenoy is then deterM

mined , using either of the ·latter instruments. When the

present instrument was constructed, it was hoped that a

larger change that would be more easily measured could be

obtained. To do this t he frequency was raised to 120

megacycles, whe re a small capacitance change would cause a

considerable shift in frequency. In addition the cell

geometry was made relatively l arge . The oell geometr y oan

- not ba.-ve-t-oo muc-h oapaoiternoetrt --thtlrf.rErquencyor tne load--­

ing will be excessive, Next the reterenoe oscillator was

fitted with a very tiny condenser coupled to a National

precision dial of high mechanical ratio. As the change

occurs in the cell; it sh11'ta t~e frequency. This ohange

1a then followed with the rere~enoe osolllator, by using

an audible beat . The instrwnent is self conta ined and no

auxillary pieces of appatatus are needed• In addition to

the above reasons f or selecting ~n instrument frequency ot

120 megaoyoles, there is the question of solution concentra­

tion. Moat titrat1ons ·use a practical concentration of .lM.

The earliest experimenters soon found that they were seriou~

ly restricted in many reactions by using very low concentra­

tions to obtain t he necessary sensitivity. The change of

fre quency of an oscillator due to the change in dieleotrio

I

15

constant of an electrolytic solution is a function of con~

centration at a particular frequency . A response can be

obtained only in that concentration region where the

dielectric constant of tho solution (and osc illator

frequency) change with concentration. The data of Forman

and Crisp (1946) allow a prediction of the concentration of

maximum sensitivity for various electrolytes . These authors

have given a simple empirical r ela tion between the concen­

tration of a solution and the frequency at which the

adsorption of energy is a maximum: lc:k, where 1 is the wave

length in centimeters, c is the normality. and k is a con­

s-t-a-nt • oha-rao-t-erts-t-ic nt-t-he~leo-trolyte-employe(l. Wi th the

use ot this formula it can be shown that the optimum

frequency tor use wi th concentrations of about . 2M woula be

approximately J60 megaayoles. However, building a stable

oscillator at t his frequency has some serious stability

p:roblems . Blaedel and Me.lmstadt ( 1950·: J) have constructed

suoh an instrument and the authors olaim that it works well. '

At 100 megacycles the opt~mum aonoentration is about . 05 M.

However, results with the writer's instrument at 120

megacycles using .1 M solutions have been very encouraging.

- c 2

w

L

16

This is the equivalent oircuit of a oapacitively

oot.lpled high-fl'equenoy oscillator (Blaodel, Halmstadt,

Pe titjean ond Anderson 1952). o1 represents the oapaoity of

the solution 1Atl. ioh remains fairly constant . R is the

resistance of the solution , inversely proportional to the

oonduotivity and varies greatly as the solution changes from

dilute to oonoentratad, but c2 is independent of the

electrolyte concentration over a wide frequency range . L

represents the inductance of the network, In the a uthor's

instrument an S•shaped cur~e is obtained if the concentra­

tion of any electrolyte is platted Vefsus the change in

freq!!_enoL_ As was pointed_ out earlier.., the oon.oentration

and sensitivity depend on the frequency. To explain this

a -shaped curve it must be realized tha t when the impedance

of R is compared to that of 02, the latter is almost shortied

out, and the frequency approaches I/2TI ~ in con­

centrated solutions .

In the case of dilute solutions, the impedance of R

is large compared to that of c2 and the froquenoy approaches

y--2 IT V<ctc2ytc.

1 C

2 • In botween these two extremes

you ha~e varying intermediate situations.

CHEMICAL ANALYSJ.S WITH THE HIGH .FRE\~UENCY OSCI-LLATOR

This seotion will be divided into several groups.

Beoauae of the uniqueness of the instrument , analysis with

t he high frequency oscillator has been ex t ended to many

tields .

Bina~y Solutions

17

One of the simplest applications of this instrument

is an analysis of a binary system. Since the response is

primarily due to dieleotrio changes in the solution , a study

of binary systems involving widely different dieleotrio

cons t ants should be int eresting . The writer o~ose wate~ and

aeo ute et yl alcohol , water and acetone-, wa t-er and dioxane,

water and aoet!o acid, water and propionic acid , and benzene

and nitr obenzene . In every oeae there was a very s i gnifi•

cant change in frequency (instrumental reeponse) as the

concentration ot the binary mixture varied• The graphs ot

these results are shewn in figure ( 8- 10) • It will be observ­

ed that although the graphs are not straight lines , the

our~aa a~e ~ery uniform. Below lo a table of dieleotrio

oonotanta of the liquids involved .

D1eleotr1o Constants at 20°0.

Acet1o Aoid • • • • • • • • • 6

Aoetone • • • • • • • • • • • 21

Benzene • • • • • • • ••• • 2. )

Dioxane • • • • • • • • • • • 2. 2

18

Ethyl Alcoh~l • • • • • •••• 26

Nitro Benzene • • • • • • • • • )6

Propionic Aoid •• • •••••• J

Water • • • • • • • • • • • • '. 80

Only miscible binary systems were investigated. Distilled

water was used end the organic chemicals were teohnioal

grade.. Pu.ritioetion was not necessary sinoe only an indica­

tion of instrumental response was sought . If the dieleotrio­

oonstants in the table are compared with the order of the

curves in the graph in tigure (9), a direct relationship

will be observed to exist.. As would be expected the largest

---di:tf~enoe--in-dialec.trio_a_on..atant oausa ELJ;he greatest __Q_hange

in frequency . Although the response .is not linear, the

results are ~ery reproducable and oould be very easily

adapted to measure the purity of solvents, the amount or moisture present, etc. The write~ is very enthusiastic over

the analytical possibilities in this area, because the

instrumental response was the gr eatest of any of the fields

of analysis tried . It should be pointed out now that the

response obtained by varying the concentration of electrol­

ytes does not follow a particularly uniform pattern. The

reason is that the change is usually not due to a ohange in

dieleatrio constant;"but is rather an effective capacity

ohange introduced into the oirouit by the shunting effeot of

the conductance on · the oirouit . The ourves of aoetio aoid

and propionic acid are easily distinguishable by the small

l9

humps at low concentration . · These are undoubtedly ,due to

the weak ionization oonstanta ·of these acids and are a com­

bination of the d1eleotr1o constant and ·tne ·oonduotanoe .

Tho literature liste aome ·tntereating ·stud i es or high

trequenoy methods in the field of binary analysis . West,

Robichaux and Burkhalter (1951) analized a statio ternary

system of water. benzene and metnylethyl ketone. Their

method involved the removal of water in the system with a

drying agent that rema ined in the cell for tho second

measurement and did not affeot the reading . West, ~anise

and Burkhalter ( 1952) de·so ribe a number of alcohol- water

syt>t ems -ino~ud-ing som pa-rtlal-l.y-.m1sc1b-l~nes a.ad--1-nolud

ing several polyhydrio alcohols. Hall; Gibson, Or1tohfield ,

Phillips· and Siebert ( 1954) used · a General Radio tw1n-T

impedance measuring circuit to s t udy binary liquid systems

and a mathematical analysi s is made of the results. The

syst em dioxane-wate~-potassium ohloride is studied

partioularly• One practical industrial application was

demonstrated by rrhomas, l!'aegin and Wilson ( 1951) of the

Humble Oil and Refining Co., Baytown • Texas . They rely on

the measurement of dielectric oonstant to monitor a stream

of toluene or xylene t o determine its purity . They used a

high frequency oscillat or in oonneotion with a oapaoity type

oell• looated in a sampling bypass tube from the main

stream.. An automatic reoordar keeps an aoourate reoord ot

the per oent of toluene or xylene in the run. Jensen, Kelly

20

and Burton ( 1954'} describe ·a ro.et.llG>d for tho determination of

moisture in salida . ·Although sodi um 'ch·lor1de and acnmoniwn

nitrate were employed ln their inves tigation the method

should work tor other compounds t 'oo·. ' Takahashi 1 Kimoto and

Yamada (1951) describe a procedure for analysis of binary

mixtures in several mixtures in several organic solvents .

Nitrobenzene .. anilina and other similar organic oompouna·s

were studied including the effect of moisture and impurities

on the accura cy of t he analysis . ' · vJeaver ,- Whi tnaok and Gant z

( ;1.956 ) of the U.·S . ( Naval rl'est St ation , . Oh1na Lake , CalifornJa,

used a Sargent Model V Osc ill ometer t o determine the mo i aJ

tU"r e-con1rent o-t-Hy-dra-ztne and-1..,1.-d-ime thy-lhydr~-z--ine . They - ¥) f ound that t he l ,!l .. dime thylhydrazine ~water s:vstem co uld be

determined acc ura t ely,. but · the water - hydrazine system c ould

not~t

Titr a t ions - The f ie l d of ptimar y interest in high frequenoy

me t hods of analys i s i s an end point i ndicator in t1tr at1ons .

The idea of performin~ a t i tration and e l imi nating any

d i r eot oontaot wi th the sol ution is very appealing and has

no doubt spurred many i nvestigator s into cons trudting an

ins t r ument and trying .tt . Moreover many titrations l a ok a

s uitabl e end point 1ndi qa tor fo~ one reason or another and

the hi gh f r equency me thod could be the answer. In gener af

t he r esponse of t he high f requency apparatus is bas i ca lly

s i milar to a conduotomet rio t itration exoept there a re no

electrodes involved. The shepe of the curve obtained

depends on many factors and will depend on such things as:

which el.eotronio variaole is being measured by t he 1nstru-

ment, we ak or ·:3 trong electrolyte, frequency, temperature, I

21

eto. But regardless of the general shape ·, an abrupt change

in the ourve repreaents an abrupt change of dlelootrio

constant or oonduotanoe (or both), and is an indication of

and end point~ I t is possible to secure sensitivities

oompareble to most conventional methods and in some cases

even exceed them. The high frequency method has now been

extended to no.n~~queous titrations and the results have

be-en-va ry-grS't-1.--t'y ing~. ---

The first experiment performed with the author's

ina trument was w1 th NaOH and HO l :t' i gure ( 1);. It will be

se.en that the slope drops and rises evenly ~ The end point

is sharply defined• The ionia reaction is :

H+ + 01- t Nat + OH ... ~ Na + + C l- t H2 0

Per mole of NaOH added• the effeot is to replace one mole

of Ht with one of Na+ before the equ1volenoe point; whereas

after the equiva lence point, the effect is to add one mole

of Na + and one mole of or( • The dielectric constant depends

1 I

on the ion mobilities and their concentration• We are re- \

placing the more mobile a+ with the slower Na+, hence the

ourve dropG• At the equivalence point we now start to add

an exoesa of t he more mobile OH- and the curve begins to

rise once more.

22

In figure (2) is given the titration curve for NaOH

and HAc (UOzH;02). The ionic ~eaotion is:

HAc t Nat + OR- • Nat t Ao~ + H20

The previous d1sousnion concerning tho HCl and NaOH also

applies here, but t he curves are not identical. rl'he ItAo is

only slightly ionized, and tll~r~ are few aotual H+ ions

present in the solution. Fer mole o·f NaOH added, we are

then replaoing 1 mole of HAo wi tih one mole of Na+ and one

mole of Ao- until the equivalence point is reached . After

this wo are just adding one mole of Na+ and one mole of OH- .

Because there is only a slight di:t':t'erenoe in ion mobility

-----n-e-t-we-e-n---'t-he---A-e~nd-Htre-t-b:e-o-tt.llve---r-!;-se s sl-ow±- • A-f~··A-r-------­

equi va le.noe the faster OrC causes the curve to rise rapidly

and it resembles figure (l ) from this point on.

Figure (J) is the t~tration Qurve for oxalie aoid a~

NaOH. The ionic react ions are:

H+ t Ho2o4 ~ .. Na+ + Oli-~H0204 + Na-+- + H2o

+ .J.:. + -HC204" + Na ' + oa · ~ Na + C20i; i H20

'l'his 'curve shows two encJ. ... points and this is expeoted. sinoe

oxolio acid· is d1basic . The first end~point is, of oourse.

one-half the oaloulated or second observed end•point.

This is analogous to the si tua ti on ob&~rved in oondl'ictometrio

ti trationa ~ T.his curve resembles both ot the two previous

durves, Before the first equivalence point, the taster

moving nt is being repleoed with slower moving Na+ and the

ourve drops . After equivalence the slightly ionized RC204•

2J

is ropleeed with taotar Na+ and the ourve ~ises slowly.

Attar the sooond .oqu1valenoe point til~ r~ater OH"" bttgL.ns to

ada and the ourvo rtaoa rapidly.

F1gtue (J.) ra.tH~&:~ents the titration ourva ot H;P04 and NaOH. I.n tho writer ' s opinion, tb1o was not ou<Joosstul. ,]

The 1nstru~ent apparently t.a1lo if tho ionization constant ~ 1& too week. A oonduotometric titration tigura (5) waa alm

run on the same aaid 1n an oftort to int6rpret the roaults.

In any e-vent it is V<n~y difficult to analyze. All· ond

points v1ere checked using phenolphthalein aa the 1nt1ioator.

/1 t1trot1on ot Ol- and AgN'OJ wan attempted. Tile

tonto r~~c~ion-fsT ----------~

Ag+ + 01 ... + Na,._ + l-lOj • l\gCl. + Na + + NOj

Detore tha ~qutvalenoe point the etfeot 1& to replaoe one

mole ot ex- wl tb ono mole ot No3- and afterward with one

n1ole . or Ag+ and one mol.e N05: .D'l'om previous experiments 1 t

se&ms that the ohange· should bG l.tlrse ~nough to bG olea.rly

det1ned a~a exper1montally 1t is praot1oal. The presence of

the preo1p1teto undoubtedly contributes to th~ general laok

ot unifo:m1 ty ot th$ ourvo ·until the ena point 1e roaoned.

The ond point waa oheokecl ua1ng a Obl'OlWlta 1.ud1oator. Other

typo& ot tittat1ons were attempte4 with this inatrum$nt,

but the roflulta wore not too &nooura61ng, several oxldatio&

roduot1on l'(H~Ot1ona were tried, with oonoontl"ationa from

o.Ol•l. o u. In every oaae the degree of raaponoe trom thla

tnstrtw~nt wa$ not sutfio1ent for ~nalyt1oal purpu&ee.

24

One other area was explored which holds the greatest

potential of any tried. Titrations in non-aqueous solvents

open many new fields in analytical chemistry and the Qetec­

tion of the end point is usually difficult. Color indica­

tors are not practical and electrodes for conduotometrio

methods a~e not always readily available. The high frequen~

method then becomes the method of ohoioe. One titration

figure (6) was run for aniline. This weak base was dissolv­

ed in glacial aoetio acid and was titrated with perohlorio

acid also dissolved in glacial acetic acid. The response

of the instrument was sufficient to indicate a sharp end

po n • The wr er wishes tliat more time were avai~atrl~~

explore this area more fully . Because of the interest in

applying the high frequency method to titrations, there are

numerous references in the literature. Dean and Cain (1955)

used dimethyl:tormamide a.s a medium to titrate acids.

Lippincott and Timnick (1956) were able to titrate aniline

and 9- substituted anilines using glacial acetio acid as a

solvent. Masui (1955) studied the titration of dicarboxylio

aoids and their salts in non-aqueous solvents such as

me.thanol-benzene and aoetio aoid•glyool. Weak organic acids

were titrated with sodium methylate in a benzene methanol

mixture by Ishidate and Ma.su1 (195:3-2) and by Jensen and

Parrack: ( 1946). Masii ( 1953) bas also titrated organ1o

bases and amino aoids in nonaqueous solution. It is report•

ed to be feasible for bases with d1ssoo1at1on constants on

1

25

the order of 10'"'1°, Hall ( l9S2) 41soussea the praotioali ty

of t he b.igh fl.'equanoy mt.hod as an end point indioator.

Blaedel and Malmstadt (1952) devised a differential method

for determining end points and in some oases obtained great­

er accuracy than may be obtained from the primary ourve.

Jansen, Wa tson and Vela (1951) used soap solution to titrate

the Calcium and ma gnesium in water as a measure or its

hardness. Goto and Hirayama (1952) used a o.l N oxime solu­

tion to titrate copper, z1no, aluminum and iron. Copper,

zinc, oaloium and magnesium were titrated with ethylene~

diaminetetraaoet1o acid by Blaedel and Knight (1954) •

. Iaeael----and~mstaij1i-ri9"5l useCI oxal-:to aol_d_ o determine

thorium. and report that it is free to error from interfering

substances that oaused trouble in t he conventional gravi­

metric procedures. Ande~son and Revinaon (1950} desoribe

the titration ot Beryllium with ammoniU.lll phosphate and I

ammonium hydroxide or sodiuf!l hydroxide. Young (1955)

studied the non•aqueous titration of strong acids, Ishidate

and . Maaui ( 1953~: l) describe the alkalimetry ot alkoloids and

weak organic bases . Chloride determinations ha~a been

studied by B~aedel and Malmstadt · (1950:2:3). Jensen and

t>arraok (1946 ); Anderson , Bettis and Revinson (1950) and

Young (19;5)• The titrating reagents used were merour1o

nitrate and s ilver nitrate~ Sulfate preo1p1tate determin­

a tions al'e di$cussed by Bien (1954), Musb.a (1952), and

Milner (1952}. Grant and fia Emdler (1956) developed a method

26

tor the determination of fluoride by titration with thorium.

Tanaka and N1ahigai (1952) evolved a m1cro~method of deter•

mining ammonia by titrating with aulfur io acid , and Kono

(1951- 52) used a mioro-Kjeldahl procedure, A similar

procedure is described by Kremen, Mathews and Borders (~949).

Complexes - s everal attempts were made to determine the

teas1b111ty of using th.is instrwnent for studying coordina­

tion numbers ot complexes. Iron was titrated with potassium I

thiocyanate, niokel with dimethylglyoxime and oopper with

ammonium hydroxide~ In all lnstanoes there was a ohange in

frequency. However, the graphs did not show any breaks that

would indicate that the method could be used for analytical

purposes. It must be remembered that the instrument can

only be suooessful when there is a significant ohange in

dieleotrio constant or oonduotanoe of a solution. Apparent­

ly there is not a sufficient difference between the metallic

ions and their oomplex ionio form. Ethylenediaminetetraaoe­

tio acid was used by Hare and West (1954-55) to suooesstully

determine caloium, nickel, copper, zino, lead and manganese.

Also for uranium (1955) Hall, Gibson. Phillips and Wilkinson

(1955) describe their work with nickel and d1methylglyox1me.

Hera (1951) studied the complexes of oopper, n1okel, zino,

iron, manganese and cadmium with pyridine, hexamethylene­

tetramine, ethylenediamine and bipyridyl. The oomplex of cL ' and p -naphthylam1ne , m- and p-diaminobenzene, piorio ao1d

27

and titan. yellow with cadmium, oobalt, iron, magneaiwn,

oaloium, barium, nickel, meroury, silver, lead, oopper were

also studied.

Reaction Rates - One other type of reaot1on was studied­

reaction rates, Results were disappointing, Alkaline

saponification of ethyl acetate was attempted at several

oonaentrati ons, but no significant change of frequency

oocured. Ester formation was tried by mixing various pro­

portions of glacial acetic aoid and absolute ethyl alcohol

and allowing it to stand tor a maximum of three days. The

mixtures were run by the binary solution method eaoh day for ' -- -- -

three days and the results tabulated to see if any slgnifi•

oant change had taken plaoe. No ohange was diaoernable .

The iodine .olook reacti on was also triad in several oonoen•

trationa , but no change was observed. Jensen, Watson and

Beckham (1951) were able to follow the saponification of

ethyl acetate. Duke, Bever and Diehl (1949) followed the

rate of precipitation of barium sulfate . Flom artd Elving

(19SJ) used the method for measuring the rate of alkaline

hydrolysis of l ower aliphatic. esters and esters of ohloro~

aoetio aoid. A recording device permitted the investigation

of half times of 10 seconds or leas .

Chromatogranhl • The literature lists one other ~ery inter­

esting applioatio~. This 1s the analysis of eluents in the

Qhromatograph1o processes . Monaghan, Moseley, Burkhalter a~

28

Nance (1952) mounted a pair of condenser plates at the

bottom of a chromatographic column and determined the

analysis of the successive elutions . Similar apparatu~ was

used by Laskowski and Pulsoher (1952) and Troiak11 (1940).

Honda (1952) uaed a coil from f:.l portion of a high frequenoy

oscillator to detect the +ocatiqn :q~ tmetallio ion banda on • ,I · :

a resin cation exchanger. Bauman an~ Bluedol (1956) follow­

ed the separation of carboxylic acids by using a oapaoity

type of monitor on the effluent stream from a chromato­

graphic column. Hashimoto and Mori (1952) adopted a

capacity type dev1oe to determine the position of various

s ubstances on paper after chromatographic separation.

29

SUMMARY

A heterodyne type high .. fJ'equency titrimater., operat­

ing at 120 megacycles was constructed.. The instrument is an

original device, combining the beat features of two previous

instruments {West, Burkhalter end Broussard 1950 and Johnson

and Timniok 1956)• and incorporating severalmnovations of

the author . It is aelf.oontainad and no auxilary equipment

1s necessary to operate the unit. The cell holder plugs

into the ob.asais with three banana plugs and oan easily be

modified Colpitts type using a 90 om~ length Of RGS/U

coaxial cable as a halt~wave resonator' After a suitable

warm up time the instrument shows very good stability. The

120 megacycle trequenoy was o.hosen because it represents

the upper lim~t of easily attained stability and still per•

mits the use of 0.1 M solution o<r,no.entrat1o.na. The instru ...

ment has capably shQwn its worth as an analytical tool by

tit~ating weak and strong a.o1ds and bases in aqueous and non­

aqueous solutions, as well as preo1p1tat1on type reactions.

In addition it ia well suited tor binary solution analysis .

In the author's opinion the inst~ument is very easy to '

operate • . This , togethel' with its versatility and stability

help make it a valuable analytioal tool in the tield of

high-frequency t1trimetry,

APPENDIX

. ! .....

7 l::j f-J·

~ p r H 1--' 0

Qp;j

~ ~ --p,? .... 1-'-~

~4

1

12 14 16 18

TITRATI ON CURVE : NhOH e-n d HCl NaOH = 0 . 10 50 N HCl = 0 . 1033 N 2 5 o l . of liC l pl us 75 ml . of \·1a ter in vesse l e:. t~ star t . Ca l culated ~nd-poiht = 24 . 6 ml .

I I

I I

I I

Obse~ved end - point = 24 . 6 ml .

20 22 24 2 6 28 30 32 ".3 4 36 Ml . of Ba se Added

\..V 0

•

I ..

10

9

8

7 '=' f-J·

l:j SD 6 H j-J

Cj) ?;j ~ (1)

l::j ~ 5 1'\) 1-'·

erg 4

3

2

1

12

TITRATION CURVE: NaOH and HC2H3o2 ~iaOH = 0 . 1 050 N HC2H3 02 = 0 . 1059 N 25 m~ . of HC 2H502 plus 75 ml . of v;at er in ves s e l a t s t a r t. Calculated end-point = 26. 2 ml .

I

I

end- point = 26 . 2 ml .

14 16 18 2 0 22 24 2 6 28 30 32 Ml . of Base Added

34 36 w ~

10

9

8

7 t:J 1-J·

~ p 6 -H 1--'

Q ~

~ [ 5 \>l ....

~

~ 4

3

2

1

4 6

TITRATION CURVE : N'aOH and H2C20 4 NaOH = 0 . 101 5 N E2c2o4 = 0 . 1050 N 25 ml . of oxa l ic a cid plus 75 ml . of ·water in vessel at start. I Calculated end- point = 24 . 2 ~1 .

j ; ·

H+ end- J oint =

Observed end- point =

12 . 2 ml .

8 10 12 14 16 18 20 2 2 24 26 28 30 lll . of Base Added

32 \....) l\)

f:

10

9

8

7 t:l 1-'·

~ p; 6 H 1-' c;:::

~ ~ 5 p. ..p:. 1-'·

~ aq4

3

2

1

4 6

TI TRATION CURVE : Na OH and H7.PO~ (High - Frequency Method ) NaOH = 0 . 1050 N · :; · H3P04 = 0 . 1070 N

25 ml . of phosphoric a cid plus ~5 ml . of water in titra tion vessel a t ct· rt. Calc~ated end- point = 25 . 5 ml .

= 12 . 3 nl .

8 10 12 14 16 18 20 22 24 Ml . of Base Added

26

Observed end­point = 25 . 6 ml .

28 30 32 w w

11

10

9

8

~ 0 7

~~ \)1 6

5

4

3

2

2 4

TITRATION CURVE: NaOH and H3Po4 ( Pot entiometric ) Na OH = 0 . 1050 N H3P04 = 0 . 1070 N

25 ml . of phosphoric a cid plus 75 ml . of water in titr~tion vess el a t s t a rt . Ca lcula ted end point = 25 . 5 ml . I

= ~ 2 . 6 ml.

6 8 10 12 14 16 18 20 Ml . of Na OH Adned

22 24

I Observed end- point = 25 .8 ol .

26 28 )0

'vJ ~

10

9

8

7 \::j ~·

1-:zj lli H l-'6 Q ·

~ ~ . 17.1 pc

I P., 5 0\ 1-'·

~ O'tl

4

3

2

1

1 2 3

Titra tion Curve: Aniline and HClO us ing glaci~l a cetic a cid as a so1vent . 1 26 mg . of aniline f ound experimenta lly . 129 L'lg . of aniline v1as di ssolved in 100 ml . of glacial acet~c a cid ut s tart . Aniline vvus s tock purity and not redis tilled .­HC104 = 0 . 2000 N

end- point = 6 . 8 ml .

4 5 6 7 8 a -' 10 11 12 13

Ml . o f HClO 4 A6.ded •. . ~

·''.·.:

w \J1

l:j H

~ -:]

0

4

0 0

6 8

TITRATION CURVE : Naal = 0 . 1000 N AgN03 = 0 . 0995 N

25 ml . of sodium chloride plus 75 ml . of water in vessel at start Calculated end-point = 25 . 21 ml . (Volhard)

n 0

10

0 0

0 0

0

14 16 18 20 . Ml . of AgNO- Added

)

n 0

0

n

0

Ob$erved,..,~nd­po~nt = .:::) . 2 ml.

32 w 0'

200

18 0

160

~

~~ 120 c;:JrO sm ~100 CDd

..-I A

100

~

BINARY MIXTURE Benzene and Nitrobenzene

60 40-Nitrobenzene Wt . %

80 20 0 \..0 --.J

200

180

160

140 t::l 1-'· ...... ("'

H H20 Q

~~ ~~00 1..0 1-'·

::s Cltl

80

60

40

BINARY MIXTURE

( 1) Water and Di oxane ( 2 ) Wat er and Ace tone ( 3 ) W~ter and Ethyl Alcoho l

.:·

( 2 )

20[ ~;::::~ I ~ ~ J -<>=P ~ I I I

100 80 60 40 20 0 \7a ter Wt . % w

CXl

__.. p, 0 1-'· ~

Otl

100

:BI:N.AitY ;;:IXTLJRE

(A) :/i:..:. ter and Aceti c Acid

( B) ·Nater c.Jld Pro !)ionic Acid

I

80 60

'.'later ',"f t . % 40 20 0

\......> ~

40

CLAPP OSCILLATOR

----- --

FIGURE 12

I

COLPITTS OSCILLATOR

FIGURE 13

XTAL

L

I ·-----·-·· ---· .. ) r-l j IB+

CHYSTAL OSCILLATOR

FI GURE 14

.----·-··---------

--··· ---i 1--

I _j

HARTLEY OSCILJ~TOR

.li'IGURE 15

RFC

41

42

~ L2

3RFC

~+ TIDTED PLATE -TillTED GRID OSCTLLATOR

FIGURE 16

STABILITY

2 t:D 1=1

·r-1 '7j m <!> ~

~ . -<>---·'\ - -- ·-0 - __ .. .J)

rl 1 m .,.., A

'"--__._ __ l_ I 1 _ L.----.J----------· 1 5 30 45 60 75

Time :Ln nlinute s

FIGURE 11

SC H EMAT IC

H IG H FhEQ UEN CY

T I TF~ IME. TER

FIC;URE 17 -------­'----- ------------·-·---

I

43

\ /

f\

i 1 t:/ lL-i----------·---.---..~_,

;:r:/\ \/ - .... _·- -····--···_. ... ~·- ·- -·-----------------·- .. -·- ------

'

! I J I,

f l . I I ;

I I

44 ~---·--·~·-------------·---·~ ---~----· ... ··---··------ _, ....... ·----- w ---··

+ m

0~ -------1 t--C>

>-_J

u Q.. - (L

>=_g5l ~-tD <:1 3 t·-

z <;: (f) 1-----l-..JI..i....____--1----=\-11----

I .__

w l.J..j :i I .. ( <r ..J 0 f.L; -

I u.. (/) -"" (' 0

J 1-- Cl

C:_ i~ ~v_.~

1--

---~ - ------------------------··-----.. --···-·-·-·- ·-··· ·· --~- ---·---

FIGD11E 18

45

LIST OF PARTS FOH HTSTRUM.l£NT AND POWE11 SUPPLY

RESI STORS I

He s is tor Ho. Value* Res i s tor No. Value*

1 4700· 19 400

2 lOOK 20 250K

3 500K 21 600K

4 600 22 50 0K

5 21\-5W 23 680

6 2K-5W 24 :no 7 50 0K 25 150K

-8 500-K 26 - 56DO

9 600 27 250K

10 50 0K 28 400

11 500K 29 7501{

12 lOOK 30 15K

13 5K-10W 31 100-2W

14 4700-2W 32 lK

15 l00-2W 33 15K

16 15K 34 5K-10W

17 15K 35 250K

18 750K 36 250K

* All resistor s are 1 watt unless speoif'ied.

46

LIST OF PARTS J.i'OR I NSTHUMJ:NT AND POVlEH SUPPLY

CONDENSERS*

Condenser Gondenser No. Value, mtd . No, Value , mf d

1 0,1 16 50-50 mmi'. (Split - atator)

2 0.1 17 1-3 mmf .

3 25 @ 25V {Butterfly)

4 10 @ 4'0v 18 5 mmt .mioa

5 10 @ 450V 19 o.ol 6 10 @ 450V 20 0.002

7 0.1 21 0.002

8 500 mm.f. mioa 22 0 . 01

9 O. l 23 .. 5 mmf , m1oa

10 25 @ 25v 24 100 mmf . mioe

11 0.1 25 100 mmf . mioa

12 100 mmf. mioa 26 100 mmf ,mioa

13 100 mmt . mioa \ 27 100 mmt' .mica

14 100 mmf . .mica 28 8 @ l+50v

15 100 mrnf. mioa 29 8 @ 450v

* All condensers 600v exoept as noted.

LIST OF PAHTS FOR INSTRUh~NT AND PO'llli.R SUPPLY

l

2

3

4

5

6

7

6

vl

V2

VJ

v4

v5

TUBF~S

6SJ7 v6 6SK7

6SJ5 v7 6L7

6H6 Vg 6SK?

O.A2 v9 955

955 V1o OA2

V11 5U4-G

COILS

Value mh.

10 ~urns No . 22 wire wound around R15

2~5

10 Turns No, 22 wire wound aroun<l RJl

2.5

2. 5

90 om. l ength of RG8/ U ooaxial cable I

90 om, 1angth of RG8/ U ooaxial oable

MI SCELLANEOUS

CH Filter Choke • 10 henries.

S S P S T

F JA

T 350-0·350 100 m. a . 5v - JA 6. Jv - 4A

47

FIGURE 19

Inetrument and Power Supply

48

FIGURE 20

Instrument • Baek view

49

FIGURE ·21

Instrument - Top view

50

51

FIGURE 22

Cell Holder • »ot;om ·Removad

RKFEHENOES OITED

Anderson, K.., Dett 1a, E. 8.. and Rev1n.aon, D., ."~table .H1gh•Froqu.enoy Oao 1llator '~ype T1tr1metel1" ~n~llti~al Cn&m~strz ~. 74) (1950)

/inc!lorson, K. an<l nevinaon, D. uuJSe ot lilgh ... Fre Q. uenoy 'r1 trim.~t~u:s." A,qa,~lt1ott .. ~ Ohemlstrz n. 1272 (1950)

Bauman, ~ . and Blsedel, W.J. · -.J\ppl1oat1on ot 1Ugh•ll'raquenoy Methods to Detaotion ot Bands 1n Part1. tion Chl•omatographyl' ~~a~x~1c~l gqemia~rl ~. 2 (1956)

Bien, a.s. "lli gb-Frequ$noy Titration of M1oro·~u.ant1t1es of Chloride end SuJ.t'ate.tt l~U$,ll~1oU CJ'tem1a~l'l ~- 909 ( 1954)

Ulaedel, W. J . and Knight , B. T. "Stoichiometry ot T1trat1ons ot M&tal Ions with D1sod1um

--------..""a'"'~-Of-rtllyleneffam1nG etraaoet.i:o o.oiO. • --------Analy~~~~ C~~m1s~r1. ~, 743 (1954)

Blaedel, v: . :r. and M~lm.etadt• a:.v~-1 .. H1gh-Froquenoy •ritrat1.otl&- A study of Instrurnants • ., Jillaly,tic~.l, pne~~Jl trl a!_, 734 ( 1950)

Blaedel, w. J . a'n<l Mal.ro.etadt , H, V. - 2 nH1gb.~Frequenoy T1 trati ons-Morourio Det<trmine t1 ons of Chloride." An~~ltloal Ohemistri ~, 1410 (1950)

Bloedel, w. J. and Mal.mstadt, u. V. -J ' "fUgh-l~'.requenoy 'l'ltrationa-A )50 Megacycle Titr1m.eter. tt J.)nalyt1o,a1 Ohem1e~ry ~. 141) (1950)

Blaed$1, W.J. and Malmsta~t, ».V. nvolumetrio DetetminatJ.on ot 'l'hor1wn by Bi gh•Frequenoy Titration. " .Anall~io~~ Oh,e~1 .. ~~.U 3}.., 471 ( 19.51)

Blaedel, W. J. and Malmetedt, lt.V. " Selecting the End-Point 1A Hish~Ftequenoy T1trat1ons" ~n!llt~oal Ch,emistrz ~. 455 (19,2)

Bl$edel, w. J., Mallnstadt 1 H,V., Pct1t.jean, D.L. and Andtu•son 1• w. K. n'!heory ot Ob.em1oal Anel1Bis by High. ... li'roquenoy Method." Anall~;o~l £llt~~1atrx ~. 1240 (1952)

Dean, J.A. and Oa1n, c., Jr., mrttrat1one of J\o1ds 1n D1mstbyltorruam1de Using U1gh­lt"~re q uenoy. " Anolyt~oal Ohomiotr[ az, 212 (1955)

. . Duke, ~· . n., a.nd Bever , H.J. anO Diehl, H. "The Uate of l,r-eoipatation ot Ha~iwu Sultate." Iowa State Oolloge Journal of Soienoo 23,297 (19l~9) ~oaJ: .Abstracts Q, 6941 \1.949) - -

Flom, O. G. and Vlv1ng, P.J. ttAppl1oot1on or U1gh ... Frequenoy Oso1lle.toro to Heaot1on Rates . " ~P!llt1oa~ 9hom1§tEl 25. 54l (195))

I

Forman, J . and Or1ap, D. "!lad 1o1'requen.oy Absol.~.Pt1on Spectra or Solutions of ~:leotrolytes." Transsot1ons ·2t the Var~d~z · Soo1u~y ~. 186 (1946)

Ga to, u. an<! lti rayama, T. "Determination ot Metals by High-Frequency T1trat1on with Oxime." Journal Chemical aooiety of Jtpan, Puro Chemistry ·Section. 73 • 656 TI952). Q!i!miog!Abs ·. i!!Ot.!~ 47lf5 ( 1953)

Grant, c. L• and Haendler, U.M. · · "Oaoillometrio Determination of Flour ide • ., An~lyt~ca~ Cpemistry ~. 415 (1956)

53

Hall, J.L. "High ... Fr4ilquonoy r.ritrat1ono-Theor~t1 oal and Praotloal A ape ots." ~na~t1onl Chemiet!Y 24, 12)6 (1952)

Hall , J .L. ond Gibson, J . A. "Iligh•Frequttnoy '.f!itrations ... A ·Br1dscs t~etb.ocl." Anallt1oa~ Chomistrl 2), 966 (1951)

Hall, J.L., Gibson, J.A. Jr., Critohtield, F. H., Pbillips,H. O., ~no Siebert , O~D. "Analysis of Binary Solvent Mixtures o1' Oonduot1ng Solutions by a lladlo-Froquonoy Method." Analyt~oal Ch~~1atrx £2, 835 (1954)

'

IIall , J • L. • Gibson, J . A., Jr. ; Phillips, u. o. snd Wilkinson, P. Ho "0onduotometr1o 'l'1trat1 on a with 01metbylglyox1rne . '' Analytical f hem1otrj( !Z; 1504 (1955)

Hl.ilf~HENCl~G OI'fEP

Hera, . n. . . "Applioat1on of Higb.•Jfrequenoy Chemical Analysis to the studies of. Metallic Complex Salts.''

54

Journal of the Ptlatmaoeut1oal s ociety of Japen 71, 1122 ( 1951) Ohemloal~belr:raots 46; 2436 (1952)

Hare, H. ~.nd west, P, W. "H1gh-r requenoy Titrat1ons involving Chela tion with Etbylenod!em1netotraaoGt1o a cid. l. Chelation Studies." Anal~ttoa Ch1mtoo Acta ll, 264 (1954). Ohomioul Ab&traots !2.· :780 (ffi5) - - .

Hara, .n. and West, P, w. "H1gh•Frequenoy T1tret1ona ~thylened1sm1netetraaoot1o lllvalont Metals." Analyt1oa Ch1m1oa Aota lf, ~be'~~ ~. 6780 ( 19,5

_Hara..,_ R. _Md_ W.o..et • ~~:1 .

involving Chelation with ao1d. 2. ~eterm1nat1on of some

No. 1,72 (1955). Chem1oal

"Hlgh•li'requency rrit ra.tione involving Chalat1.on with F. tnylened1am1netetraaoctio noid. J. Det$rm1nat1on of Uranyl loll." .Analyt1oa Chim1oe Acta Mi No. J, 285 ( 1955). ChemS.ool A~stra9t~ £i, 10127 (19

Hashimoto, Y. and Mori, !. "tUgh•lfl!oquenoy Fupygraphy • an Apparatus t or Deteotlns Subatanoeo on a f1ltar paper by means of High•Fraquonoy Oaoillotors." Journal of t ne Plulrm.aoeut i,oal Boc1oty of j'jpesn 72 • l5J2 lT952) ~ CnCinrool ~traot~ lil• 1434 ( 195 -

Ish1dote, M. an~ Masu1, N.~l "fi1gh-li'requenoy '1:1tr•t1ons. 6. Alkalimetry and f\ lkalo1de and soma Organio Bases." . . Journal of ~ Pharmaoeut1eal Sooietl ot faDan Zl, 667 (1953) Chemio~ Abstraota ~. 12755 1953

Ishida to., M, an4 Ma.sui, M. •2. . "liigh•'V't'Gquenoy Tit ra tl ons 7. Tit rat 1 on in Non•/)(lUeous Solution. 1. Titration ot Organic Aoids. " Journol ot tho Pharmaoout1oal Society of Japan, Zl, 487 (l95J} Cheillal ~bsyao' Jil. 7)6) (1953)

Jense.n! .P' .w., Kelley , M. J, and Burton, M • .B ., Jr. "Mod if · od lUgh .. Froquoncy . A.P,9flra·tue for the Determine t1on of Moisture in Solids." ~.n~-) ~l~1Qal QaemiPtp:r ~. 1716 ( l954)

JentHm. T! . vr. and Y.'a.rraok , A.]'.,. ''Use or High-b'req,uency Osc 1llato.ra in T1 tra ti on and .Analyse a. 11

Industrial ~ ~noer1ns Ohemistrz, Anolytioul ~dition IlJ, 5~3 "[I946 l - . - ---Jensen~ F. ~~ . • Watson, G.M. and Beokllam, J.11. "Study of Snpon1t1Qot1on rteaotion Htr~te ot !~ thyl Acetate A.~alY;~io,al C~eD\istrl ll• 1770 ( 1951)

Je,neu~n, Ji', W. • \'/ataon, C}. ?-1 . ana Vela , LoG. "1!1gn-r req_ue.noy •ritl'et1on of Oelo1um una Mafbneslum. Ions 1n 1\queous Solution." Analr.t1cal Chemtotrx &l, 1)27 (1951)

Johnson, .A . H. a.nd 'r1mn1ok , A. "Stable H1611•11roquenoy Titration J\pparatus 1n the 100 Mo . »\requenoy Range." Anal.ztioal Chf;l.rp.\_a,trx ~. 889 (1956)

Kono· 'l'. --••Appi1oat1on ot IUgh ... Frequenoy O.soi,llators to the Stuay of Chem1oal Raaotions." Journal of Agr1oultu~_ Ohem1atry noojlety of Japan ~. 56? (l95l- ;2r- Ohemloal ~betr~~l 21, 6)01 195J).

Kremen, S, . B.,; Mathews , t . M. end ;Borc1ora, O.H. "'r.he Potentialities of lUgh ... Frequenoy Instrumentation fo~ Tunning Roaearoh Oontrol. " Journal limer1oen l.eother Chemists' J\eaoolation ~ 459 (1949) Chomloal Abatraot ~, 6181 (1949)

I

LL\akowsk1. D. hl . ana Pul~aher, R.E. nv1o1eo trio l;nd ion tor f Ol', Colttmn Chromo tography. n Analxttoal Cnemiatrl ~. 1690 (19)6}

' Lipp!Qoott, W. 1\ end Timn1ok , A. "ll1gb .. Frequenoy Titration of oome flubst1tut0d Aruslines in Glacial .A oet1o Aoid. u

~lyt~oal O~om~a~rl ~. 1690 (1956)

Maaui , M-. '*lligh•Frequenoy 'r1trot10th 9. T1tret1on in Iionaquoous Solution·, 2, Titration ot organic Bases end Amino .Aoids. " Journal ot the Pharmaoeut1oel Sooiety ot Jepan ~ lOll ( 195)) . . .G.Q.o~l. lil!.§~J:f!(lt.J.t..8.- 1895 ( l9ffi

55

56

al!:ll'l~HENOES Cl'lliD

Maeul . M. "High Frequency T1trat1one·. l)·. Interpretations of the iL'1trat1one ourvea or Oio arboxylio Aoids in Non-Aqueous High Frequency Titrati on. tt Journal of the Pha r muoeut1oal Soo1(i~ of Japan 75, 1519 (l95S) Ohemioal Abetr~ iQ, 4102- 500 --

Milner. 0. 1. " '21 tra tion ot Sulfa ta with tbe A 1d ot a High-Frequency Oao 1lla to». n

Analyt 1o~l Ches1!t£! ~. l247 (1952)

Monagbo.n, P.n., Mosely • P. B., burkhalt~r. T.s. and Nenoe, O.A . "Detection of Chroma tographic t onus by Means of Uigh• Frequency Osoilletors." Anall~ioal Chemistrx 24, 193 (1952)

Musha, s. _ "Applioatione of ~J!"r__e.queno-y !JM.tra-t-11> • :2.- Anilys1s -~r-~alL Amounts of Dulfate and its Application to tho

De teotion of s ulfur in Irons &nd Sto~le." Soientltio Reports Hesearoh lneti tutes. 'r ohoku University Se~. A, 4, 575 (l952f;--Chem1oal 1\ batr~o~ ~. 9847 (l95J)

'rakahas.hi, T. , Ki moto, K~ a nd Yamada , T. P.Qrganio Analysis by Means of Dialootrio Oonatant Doter­min& tion." . Journal ~ the Chemical s ociety of Japan, Industrial Ch~mio el aeotioa ~. 427 (1951) Cqe~~o&l Abatra~ ~. 5195 (195))

Tanaku, N. and. Niahiga1 , M. "ll18h !i•requenoy Titrationa, l, An Application to the Determination ot Traces or Amo1on1a. '' Roports Qt. the Inst1tl.lte 2.t ~oielloe and TeohnolO..BYt Un1vorsity ot Tokyo 6, l)l ~l952) C4omioal Abst~ao.t ~. 1540 (195))

Thomas. B.w., Faegtn, F. J . and Wilson, G.«. noieleotr1o Constant i\1eaauremen.t tor Cont1nuoua Determ1nati.on of Toluene." Anallt1o6l Ohem;~tr~ £l, 1750 (1951)

----

TroitekU .• G. v. "Separation ot Adsorption ~~ones . of Colorless Sub&tanoos in Chromatographic J•nulysia by Measureroont of l>1e leotrio Constant." B1okh1m1ya 5, 375 (1940) OheDlioal .. 1bstraot Ji, 7494 (1941)

weaver, R. D., Yihitnack, o,c. end Gantz, £.s.c. "Detormlnation ot water in 1,1-Dimethylbydra~ine and Hydl'ez1ne by a Hisll Frequ$noy Heth.ocl." Analytical Ohomistrt ~. 329 (1956)

West, P. w., Bur.khaltar, fj,•. s. and Broussard~ L. "High .. Frequ.enoy Oaoillator Ut ilizing the Hetsro<lyne Pr1no1plo." An~lltioal 9h~mie tr,t .3a, 469 ( 1950)

57

~.'est, F.w., Robichaux, '1'. and ~urkh~lter, '£. 3 . "Analysis ot the s ystom Water-Benzon~·l.!ethyl .li.thyl Ke tone by Means of .a lUgh- Eraqne.uoy Oaoilla tor " - - - -Analytical ~Jlem1s.-tl;;f- 3itl6-2r l1lJ3Il

west, p.w., Senise, P. and Burkhalter, 'l' . ~:~ . "Determine t1on ot .'Ia ter in Alcohols '' Analytical Chamfatrl ~. 1250 (1952)

Young, J.P. "Uoma Applloat1ons ot Ph. D. 'rhea is t Indian~ .!Q., 721 (l95o)

High ... l' .. .requenoy 'I'itr1metry." University (1955) Chemical Abstract