rd  - 1962 - ENC Conference

3 rd - 1962 Pittsburgh 

Chair: David Grant 

Local Arrangements: Gus Friedel 

“Third Conference on Experimental Aspects of NMR Spectroscopy” 

[T.C.O.E.A.O.N.M.R.S.] 

How Sweet It Was! My reflections on the early ENC Conferences (which were held for a decade 

in Pittsburgh) include three dominant memories: 

First, the format of the conference was more of a panel discussion than that of a formal 

lecture. The speaker’s comments and audience discussion and remarks were merged into 

short debates and idea sharing. These sessions, although heated at times, never seemed to 

interfere with an expanding camaraderie. The size of the group undoubtedly illuminated the 

need for formality. 

Second, the meetings solidified a rapidly growing community of NMR spectroscopists into a 

cohesive group of friends, unified by the taxing experimental challenges that all faced in 

these early days. When one discusses the problems of swinging metal restroom doors on the 

other side of the wall from the magnet lab, one knows the field is its initial stages. The 

group was small enough that discussion continued often late into night at Samreny’s, the 

Ranch, or some other restaurant in the vicinity of Mellon Institute. 

My third recollection deals with the inclement weather in Pittsburgh during the last few days 

of February and first few days of March, typical times for the early meetings of the ENC. 

To fly out of Pittsburgh always seemed to pose a problem like sleeping on the airport floor 

for an early morning delayed flight, etc. Such was the case on Saturday, March 2 nd 1961, 

the concluding day of the second 

conference chaired by George 

Slomp. All flights had been 

cancelled for the evening of that 

day, and I had to be in Columbus 

that night. I expressed my 

congratulations to George for an 

excellent program, and to be 

pleasant indicated that I would be 

happy to assist in any way 

possible to keep the tradition now 

started for future years. This 

forced a bus trip during the 

business session requiring that I 

leave around 3-4 PM and travel through West Virginia and into Ohio. There were numerous 

delays, but we finally arrived around 10 pm, long overdue and fatigued by the ordeal. Upon 

my return to Utah the next week I was chagrined to find out the hazard of leaving the 

meeting early was to be elected to chair the meeting the following year. Apparently, 

everyone wanted the group to continue meeting, but only if someone else would do the 

work. Fortunately, Gus Friedel, at the US Bureau of Mines near Pittsburgh, and the 

resonators at Mellon Institute provided outstanding support as the arrangements committee,

and many stepped forward to chair a variety of sessions and other duties. The vendors aided 

with expenses. 

For these early meetings, there were no formal abstracts, but many individuals brought printed 

hand-out material, often many pages with great detail. For the 1962 conference – with the lengthy 

name and abbreviation given above -- these notes, now available in the conference archives on the 

web site and the DVD, give a reasonably complete summary of the proceedings. The talks by 

James Shoolery on absorption mode 13 C spectroscopy and slave recorders stand out to this writer as 

truly seminal work of great timeliness in the third annual conference. Jim was truly the chemists’ 

advocate for NMR methods in these early days and his data are typical of his unique signature on 

the field. 

Equally impressive presentations were also made by other contributors, but space limitations 

prevent a detailed review of the 40-50 talks. However, the titles of the eight sessions, each chaired 

by an authority in the field, give a good idea of the scope of the conference: 

Paul Bender: New Experimental Applications and Techniques 

Paul R. Shafer: New Instrumentation 

Stan L. Manatt: Spin-Spin Decoupling 

Tom Beukelman: Spectrometers of the A-60 Type (Field Frequency Lock) 

Wayne Lockhart: Instrument Trouble Shooting 

David W. McCall: Relaxation Phenomena and Measurements 

Charles W. Wilson, III: Wide Line N.M.R. Instrumentation & Operation 

George Slomp: Interpretation, Storing and Cataloguing of High Resolution N.M.R. Spectral Data

8:15 A.M. 

9:00 A.M. 

9:15 A.M. 

I0:30 A.M. 

I0:45 A.M. 

12: 00 Noon 

2:00 P.M. 

3:15 P.M. 

3:30 P.M. 

6:15 P.M. 

7:15 P.M. 

8:30 A.M. 

9:15 A.M. 

i0:30 A.M. 

i0:45 A.M. 

12:O0 Noon 

2:00 P.M. 

2:00 P.M. 

THIRD CONFERENCE ON ~ ASPECTS OF N.M.R. SPEC~COH 

TO BE HELD AT THE MELLON INSTITUTE, PIttSBURGH, I~NSYLVANIA 

Registration 

WelcQme and Oreintation 

MARCH 2 and 3, 1962 

PROGRAM 

FRIDAY - MARCH 2, 1962 

ist Session: New Experimental Applications and Techniques 

Chairman: Paul Bender, Department of Chemistry, University of 

Wisconsin, Mad/son, Wisconsin. 

Coffee Break 

2rid Session: New Instr~entatlon (Probe Modification and Temperature 

Control, etc.) 

Chairman: P. R. Shafer, Department of Chemistry, Dartmouth College, 

Hanover, New Hampshire. 

Lunch 

3rd Session: Spin-Spin Decoupling 

Chairman: S. L. Manatt, Jet Propulsion Laboratory, California 

Institute of Technology, Pasadena, California 

Coffee Break 

4th Session: N.M.R. Spectrometers of the A-60 Type (Field Frequency 

Control - Quantitative Measurements, etc.) 

Chairman: T. Beukelman, Jackson Laboratories, E. I. du Pont de 

Nemours and Company, Inc., Penns Grove, New Jersey. 

Social Hour 

Dinner 

Business Meeting 

SATURDAY - MARCH 3, 1962 

5th Session: Instrument Trouble Shooting 

Chairman: Wayne Lockhart, Varian Associates, 611 Hansen Way, 

Palo Alto, California 

Coffee Break 

6th Session: Relaxation Phenomena and Measurements 

Lunch 

Chairman: David W. McCall, Bell Telephone Laboratory, Murray Hill, 

New Jersey. 

7th Session: New Wide Line N.M.R. Instrumentation and Operation 

Chairman: Charles W. Wilson, III, Union Carbide Technical 

Center, South Charleston, West Virginia 

8th Session: Interpretation, Storing and Cataloguing of High Resolution 

N.M.R. Spectral Data 

Chairman: George Slcmp, The UpJohn Company, 301 Henrietta Street, 

Kalamazoo, Michigan

B 

o 

C 13 NMR Studies Using 

the Absorption Mode 

J. N. Shoolery, Varian Associates, Palo Alto, California 

Due to the long thermal relaxation times associated with C 13 nuclei, 

it has been customary to study natural abundance samples with the adiabatic 

rapid passage method. This gives a signal proportional to Mo, the static 

moment/unit volume, while the absorption mode gives a signal proportional to 

~ 7~ for slow passage conditions. Rather considerable line broadening 

ccurs as a result of the high r.f. power required for adiabatic conditions 

and this not only obscures the smaller splittings due to spin-spin coupling 

but makes it difficult to interpret overlapping multiplets. 

The need for a large sample is a result of the 1.1% natural abundance 

of C 13. Until recently it has not been practical to spin a large sample under 

conditions of very high r.f. amplification because the rotation of the sample 

introduces a varying coupling between the transmitter and receiver of suffi- 

cient magnitude to overload the detector. A static sample results in T 2 be- 

ing about two orders of magnitude shorter than T I. With modulation techniques 

which have been developed for stabilizing the baseline to permit integration 

of spectra, spinning a large sample is now practical, since the NMR signal 

is now observed as a modulation on the r.f. output of the receiver coil. Less 

r.f. gain is required because the signal can be amplified in a subsequent audio 

amplifier, and r.f. fluctuations at the spinning frequency can be distinguished 

from the modulation frequency through use of a phase sensitive detector. 

An instrument operating at 15.085 mc/sec in a magnetic field of 14,092 

oersteds was employed in this work. A special receiver coil was constructed 

by winding a coil on the inside of a cylindrical glass support with i.d. of 

14 mm. Thin-wailed cells were obtained from the Wilmad Glass Company, Buena, 

New Jersey, with i.d. of ii mm and o.d. of 12 mm. A plastic spinner obtained 

from the same source provided a satisfactory means of rotating the cells at 

about 30 r.p.s. A cylindrical teflon plug was made which could be fitted into 

the cell at the liquid interface to prevent formation of a vortex. With this 

arrangement it was possible, by careful adjustment of the Homogeneity Control 

Unit, to achieve an effective T 2 of 2-3 sec., observed by the exponential os- 

cillatory decay following the signal from a strong, single C 13 resonance line. 

The signal-to-noise situation is made still more tolerable by the fact 

that more than adequate resolution is achieved without the necessity of meeting 

the slow passage conditions. Under the non-adiabatic rapid passage conditions 

actually used, the role of T I in repopulating the lower energy levels is not 

as important; i.e., we can use more r.f. power and leave the nuclei in a par- 

tially saturated condition, at the expense of some line broadening but with a 

gain of signal strength. Sweep rates of about i cps were used for most of

C 13 NMR Studies Using 

the Absorption Mode 

_ 

J. N. Shoolery 

this work which resulted in spending a small fraction of T 1 in observing 

each C 13 resonance line. 

A standard integrator accessory was used which employs 2000 cps field 

modulation. Instead of obser*ing the center-band signal as with protons, 

the side-band signals were recorded. This made possible a much lower index 

of modulation. Center-band signals can be suppressed by adjustment of phase, 

while second side-band signals are lost in the noise, due to the low modula- 

tion index. Thus, no interference is caused by the modulation unless the 

interfering signals are 4000 cps (400 ppm) apart. 

With this apparatus, previously unresolved spin-spin splittings were 

readily observable. Fig. i shows the spectrum ofacetic acid. The C 13 in 

the carboxyl group is found to be a quartet with spacing corresponding to 

J = 7.5 ! 0.5 cps, due to the protons on the adjacent carbon atom. The di- 

rect JCH coupling is 132 cps. 

Fig. 2 shows the spectrum of ethanol. The methyl carbon is split into 

a quartet with a 125 cps coupling to the attached protons, and less than 2 cps 

coupling to the methylene protons. On the other hand, the methylene carbon 

shows a 140 cps coupling to its own protons (enhanced by the attachment to oxy- 

gen) and a 4.5 + 0.5 cps coupling to the methyl protons. The chemical shift 

between the two carbons is 38.5 ppm. 

An excellent example of the data obtainable in this way is found in pyri- 

dine. Fig. 3 shows the spectrum with the ~ carbons falling at the highest field 

value, the y carbon 11.8 ppm to lower field, and the ~ carbons 26.0 ppm to lower 

fields. The direct CI3-H couplings are 180, 157, and 160 cps for the 5, ~, and 

y carbons respectively. The ~ carbons are coupled to two other protons, prob- 

ably the ~ proton and either the ¥ or the other a proton, with coupling constants 

of ii.0 and 6.2 cps. The ~ carbon is coupled abort equally to the ~ and ¥ pro- 

tons with J = 8.0 cps. Finally, the ¥ carbon is coupled to the ~ protons with 

a 5.8 cps coupling constant, and is apparently not coupled to the a protons. 

Chemical shift measurements and initial location of the peaks would be 

improved by collapse of the spin-spin multiplets to a single line by double ir- 

radiation techniques. Since apparatus for this purpose was available, the exper- 

iment was tried with a 4 mm sample of methyl acetylene enriched to 50% C 13 in the 

methyl position. The spectrum with and without 60 mc irradiation is shown in 

Figure 4. In addition to the signal-to-ncise enhancement of 16/3 due to the col- 

lapse of the 8-1ine multiplet, there is an additional Overhauser amplitude enhance- 

ment of 1.5 due to relaxation of the C 13 nuclei through the proton magnetic mo- 

ments. The effect may be greater than 1.5 and could best be measured from the 

integral, since the collapse of the multiplet does not appear to be complete at 

the power level used.

FIG. 3 

FIG. 4 

180 

i 

Jc-oH =11.0 cps 

JC.;.C.H= 6.2 cps 

I 

-26.0 ppm 

C ~3 NMR SPECTRUM OF METHYL 

ACETYLENE (C~3H3-IC12---C ~2H ) AT 

15.085 mc/sec WITH PROTONS 

IRRADIATED AT 60 mc/sec. 

ordn ry 

~--~ ..... :pectrum\ 

C :~ NMR SPECTRUM OF PYRIDINE 

(Natural abundance) 

(15.085 mc/sec.) 

I 

Jc-c-H=SJBcps I =B.Ocps 

II 

Y ~ 

I I -H-- 

-11.8 ppm 0.0 

...with irradiation 

Jc-~ (cp5)

DARTMOUTH COLLEGE 

~EPART.~IEXT OF OHE~ISTR~" 

HANOVER • NEW HAMPSHIRE 

Insert Construction for Nl~ Probe 

io Place the coax fitting and the insert tube (note i) in the jig. 

2. Wind uninsulated, oxygen free~ high conductivity copper wire 

(OFHC, 30 gauge) around the tube° Space the turns with fine 

thread and secure the ends under tension from rubber bands. (note 2) 

3. Warm the tube to about 60 ° and apply a very thin layer of epoxy 

resin (note 5) so that it flows evenly around wires and thread. 

~. Heat briefly (about 2 minutes) at IOO ° until the resin is tacky, 

remove the thread and apply a second coat of resin~ using the 

minimum amount to get a uniform coating. Bake at iOO ° for 

thirty minutes° 

~o Bend the free ends of the wire~ slightly separated, down to the 

coax fitting9 secure with Scotch Tape~ coat with resin and bake. 

6. Trim one lead to just reach the "dimple" depression and solder 

with a minimum amount of solder and heat. 

7. Remove from the jig, bend the second lead smoothly under the 

bottom of the insert to the center, and then do~mo Trim short so 

that when the tip of wire is inserted into the pin jack and the 

parts are assembled, there is no excess wire and it lies smoothly 

in the groove without touching the metal case of the coax plug. 

Solder the lead to the pin jack and assemble° 

8° Coat the bottom of the insert tube with epoxy resin (note %), 

press the tube into the coax plug and place the assembly in the 

jig. Remove excess resin to give a smooth joint and bake until 

the resin has set° 

Note s o 

i. Clean the insert tube with trisodium phosphate solution, water, 

aqua regis, water and then ammonia, in turn, and bake to dry. 

2o For proper balancing, the coil should be tipped very slighly 

rather than being exactly perpendicular to the axis of the tube. 

The wire can be obtained from various sources, one of which is 

Sigmund Cohn~ 12~ S. Columbus~ Mt. Vernon, N.Y. 

3. Ciba Araldite Resin 6010 cured with hardener Araldite HN-9~I, 

available from Do Ho Litter Co.~ Inc., PO Box 247, 30 Lowell 

Junction Road, Ballardvale~ Mass. 

4. Any commercial resin with a non-metallic loading, such as Hysol 

or One-Ton etc. The Ciba resin might work but it is claimed that 

the addition of an inert filler improves dimensional stability 

over a wide range of temperature change. 

8-1-61 Paul R. Shafer

Insert Tube for Variable Temperature N~/:R Probe 

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io Flat, closed end. Maintain OD to fit into lip of coax fitting. 

2. Space three holes at about 120 ° around the tube, each about 2 mm OD. 

Maintain tube !D to give clearance for the nylon bearing. 

3o Fire polish very lightly. 

%. Material: 8 mm OD pyrex tube, standard wall. Select ID to give 

slip fit with the nylon bearing. 

Coax Fitting for NNIA Insert. (Not to scale) 

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i. Cut off, then face down to length of coax plug on a standard 

insert tube less 1 mm. for depth of rim. 

2. Cut out faced off end to depth of about 1 mm. Make the ID of the 

rim to slip over the end of the insert tube. 

3. Shorten the pin jack until it is just flush with the surface when 

it is pushed into place. 

%o Cut a groove for 30 gauge wire (flush) from the pin jack hole to the 

rim, notch the rim, and continue the groove down to one of the 

"dimple" depressions on the side of the plug. Cut this portion 

of the groove to the depth of the dimple. 

8-1-61 Paul R. Shafer

,f, 

F. 

Construction details for N.,',,:R insert coil winding jig. 

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i. Mount end support A rigidly to bottom plate D. 

2. Mount end support B on slide F which moves between guides G-G'. 

3. Drill holes C-C' co-linear to fit insert tube (ca 8mm OD). Enlarge 

hole C to fit coax plug. Fit each hole with an end plate. 

~. Side posts E-E', mounted rigidly to D opposite the coil, serve as 

(a) tie points for the coil and (b) terminus points for the 

tension springs H-H' which hold the insert assembly in place. 

~. Space posts E-E' far enough apart so that a length of wire a' = a 

can be secured to each side . Then when the rubber bands are cut 

loose the leads will be free of kinks. 

6. The scale is about one-half~ the overall length is about i~ cm. and 

the dimmensions are not critical. The materigl is wood. 

8-1-60 Paul Ro Sharer

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SLAVE RECORDER FOR AN ~4R SPECTP.OIdETER 

James N. Shoolery, Varian Associates, Palo Alto, California, and 

Richard W. Mattoon, Abbott Laboratories= North Chicago, Illinois 

Presented at the Third Conference on Experimental Aspects of NMR Spectro- 

scopy, Mellon Institute, Pittsburgh, Pennsyivanias March 2 and 3, 1962 

~t is often very useful to have a slave recording reduced in size from 

the master NMR spectrum and available simultaneously with it. This 

eliminates the delay in cb=aining a reproduction of the master spectrum. 

Also, a good slave recording on standard 8 I/2" x II 'I paper is conveni- 

ent as a secondary record for reports and for an auxiliary research 

file. The master spectrum for the Model A-60 ~[R spectrometer measures 

ll" x 26" overall with the graduated chart space 25 cm. Y-axls, 50 + 2 cm. 

X-axis (9.8" x 20.~'). 

METHOD I,L SLAVE X-AX~S TIME SWEEP 

In ldethod I. a Moseley X-Y recorder, Model 3S, using 8 II~' x II" graph 

paper (graduated in inches in Figure I only by chance) was covmected 

to the A-60. The two AHP/INT OUTPUT terminals on the rear of the A-60 

console were connected to the two Y-axls input terminals of the slave 

recorder. The Y-axis gains were set to give appropriate amplitudes. 

Each recorder was cet for its own internal 500-second full X-axis 

sweep. The A-60 was adjusted to put the SiMs 4 line on the right-hand 

0 of its X-axis (chemical shift). Since this slave recorder time- 

sweeps only to the right, both recorders were set on the extreme left 

and started simultaneously. 

Figure i shows that the slave recording is a practically perfect repro- 

ductlon of the masker recording even for the small background ripples. 

The strong peak at 60 CPS (I,0 PPI0 is a doublet at highest resolution 

(evident here as a slight shoulder) and this is reproduced in the 

slave recording. The slave recorder reached its right-hand limit a 

little before the A-60 and so on the slave recording the SIMs 4 line is 

to the right of the edge of the graduated portion of the paper. X-dls- 

placements in Figure I between corresponding peaks on the master to 

those on the slave give a ratio varying between 1.89 and 1.93, averaging 

1.91. The disadvantages of Method I. are the inability (I) to sweep 

to the leftp (2) to independently set the SIMel. line exactly on the 0 

of the slave and keep the two recorders so-syn~hronlzed,o,- and (3) to 

have the ratio of the two X-axes 2,00 exactly.

-2- 

METHOD II. SLAVE X-aXIS SYh~HRONIZED WITH 14ASTER 

In Method II. a Moseley X-Y recorder, Model 2 (II" x 17", larger than 

required here), was connected to the A-60 with the Y-axis connection 

as above; the X-axls was connected to the center arm of the 1.15 ohm 

sweep potentlomzter located underneath the A-60 recorder, The slave 

recording was made on 8 I/T' x ii" paper graduated in millimeters 

(18 cm. Y-axls, 25 cm. X-axls). Since the X-Input inpedance of the 

slave recorder is many thousand ohms on the I volt range, no effect is 

observed in connecting it to the 1.15 ohm sweep potentiometer. The 

X-axis positioning control and the X-axis gain control of the slave 

recorder appear to interact. To put the SIHe 4 llne on the 0 of both 

recordings and also have the master X-displacements exactly 2.00 times 

those on the slave required an Iteratlve procedure of adjusting one 

control and then the other. Three adjustments of each control, re- 

quiring about one minute, were sufficient to do this. The two recor- 

ders then remained perfectly synchronized. 

Figure 2 shows again that the slave recording is an excellent duplica- 

tion of the master recording, but this time the two SiMe 4 lines are on 

the 0 of the X-axes. The master-to-slave X-displacement ratio it Fig- 

ure 2 now ranges between 2.00 and 2.04, averaging 2.02, and this aver- 

age ratio can be adjusted even closer to 2.00. On the X-scale of the 

master 1 mm. is I cycle per second and on the slave it is 2 cycles per 

second within II error. Thereby, chemical shifts in cycles per second 

may be read directly also on the slave recording from the mm. gradua- 

tions. Method II°avoids all three disadvanteges of Method I. listed 

above. 

For the Method Z. tests acknowledgment is made for the kind coopera- 

tion of Dr. R. T. Dillon of G. D. Searle & Co. and the F. L. Moseley 

Co., represented by Crossley Associates.

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On the Use of Amplitude Modulation in Measuring Large Chemical 

Shifts and in Producing Sidebands for Spin Decoupling Experiments. 

L. G. Alexakos and C. D. Cornwell 

Department of Chemistry, Univsersity Of Wisconsin 

Madison, Wisconsin 

Two common methods for generation of sidebands used in measurement 

of frequency separations in NMR spectra are a) modulation of the field 

by injection of an audio voltage in the sweep coils and b) frequency 

modulation of the RF generator. The first of these is generally 

satisfactory at low audio frequencles~ but fails above about I000 c/s~ 

probably because of attenu~tlon of the modulating field by eddy currents 

in the probe. A further inconvenience associated with this method is the 

need for using widely different modulating voltages at different modulation 

frequencies on account of the inductive reactance of the modulation coils. 

Method (b)~ frequency modulation of the RF generator, may be used at 

higher audio frequencies. With this method~ however# an error can arise 

if the carrier frequency is shifted by the modulation. If the measurement 

is made by placing sidebands on either side of the line 3 this error can 

become very serious at higher modulation frequencies 3 since relatively 

large frequency deviations are required for the generation of sldebands 

of adequate amplitude when the modulation frequency is high. Thus with 

the frequency modulation system of the varian ~310C Spectrometer# we have 

observed a substantial shift in the position of a fluorine resonance line 

as the amplitude of the modulation voltage is changed. The change in 

average frequency of the RF generator as measured with a frequency counter 

was found to be well over I00 c/s. A similar observation was made with 

the ~II spectrometer. 

We have employed pure amplitude modulation of the RF generator for 

the measurement of splittings over a very wide range of modulation 

frequencies~ with excellent results. The circuit arrangements used in 

the V4310C and V~311 are shown in Fig. I (a) and (b) respectively. The 

modulating voltage is introduced at the grid of a multiplier stage, at 

a point well isolated from the ascillator itself. 

Sidebands~ generated in this manner show little change in amplitude 

as the modulation frequency is changed from 20 c/s to 60 kc/sec at a 

constant modulation voltage. (The lower frequency limit could presumably 

be reduced by increasing the sizes of the coupling capacitors.) As would 

be expected for pure amplitude modulation I no effect is detectable in the 

frequency as measured by a counter except for the expected decrease in 

apparent frequency observed when the percentage modulation approaches 

I00~ at which point some of the cycles are "missed" by the counter. 

Frequency spllttings from several hundred cycles to over 40 kc/sec have 

been measured with this method with excellent reproducibility. Consistent

-2- 

results are obtained even with a large percentage modulation and a very 

distorted modulation envelope, since the carrier frequency remains strictly 

constant even though the apparent average measured by a counter decreases.

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SPIN DECOUPLER 

by 

Daniel D. Elleman and Stanley L. Manatt 

Physical Sciences Division 

Jet Propulsion Laboratory 

California Institute of Technology 

Pasadena, California 

The spin decoupler which is shown in the figure employs a 

phase detector quite similar to that used in the Varian integrator 1. 

(i) LeRoy F. Johnson, "Operation of an NMR Integrator System," is 

"NMR and EPR Spectroscopy," by Varian Staff and Consultants, 

Pergamon Press, 185 (1960). 

The IN216 diodes used in the phase detector are a matched 

pair and are imbedded in a copper block to maintain them at a constant 

temperature. Ten turn pots have also been used in the phase shifter 

and audio amplitude section so as to give a little better control in 

these settings. Also, 0.022 ~f capacitors have been placed at the 

output to the sweep coils to attenuate the modulation. A switch, not 

shown in the diagram, has been added so that these capacitors can be 

shorted so the full output of the audio amplifier can be placed on the 

sweep coils.

A pre-amp has also been added to give some additional gain 

at the phase detector. A General Radio Sound Analyzer, Model 1554A, 

is placed in front of the pre-amp. The Sound Analyzer acts as a narrow 

band filter that can be tuned to pass only the decoupling frequency. 

The analyzer has a band pass of approximately 3%. 

A set of capacitors has been added across the output recorder 

gain pot. These capacitors act as a filter and can be set to give any 

desired time constant so as to reduce high frequency noise at the output. 

One must remember to by-pass the RC filter network on the V4311 spectro- 

meter@ If this is not done, the audio signal to the phase detector is 

attenuated. The most convenient method of by-passing the filter network 

is to set the spectrometer on WL ~ mode of operation. 

With this decoupler we have been able to decouple spin systems 

that have coupling constants greater than 50 cps and chemical shifts over 

9000 cps. The smallest frequency that we have set the decoupler is 40 cps. 

At frequencies smaller than 40 cps, the signal to noise becomes very bad. 

Additional details of the operation of the spin decoupler are given in 

a paper which will appear about April 15 2. 

(2) D. D. Elleman and S. L. Manatt, J. Chem. Phys. (in press).

• 3 

Samples of proton 3'4 and fluorine 5 of spectra obtained with 

(3) S. L. Manatt and D. D. Elleman, J. Am, Chem. Soc.,8_~., 4095 (1961). 

(4) S. L. )kmatt and D. D. Elleman, J. Am. Chem. Soc., (in press). 

(5) D. D. Elleman and S. L. Manatt, J. Chem. Phys., (in press). 

this spectrometer can be found in other publications 6. 

(6) All recent Jet Propulsion Laborator~ Research Summaries.

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MESITYLENE

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OF N,N-DIMETHYL-p-TOLUID|NE 

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CH 3 

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; CH 2 

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z/2:33.813620 Mc/s 

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o b c 

CI3(H I) SPECTRA OF n- HEXANE 

CH3CHzCi- 

c b a 

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a b c 

AT 8.502508 Mc/s 

a) 33.812880 Mc/s 

b) 33.813220 Mc/s 

c) 33.813500 Mc/s 

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NMR PULSE SYSTEM 

by 

S. Meiboom 

Bell Telephone Laboratories, Incorporated 

Murray Hill, New Jersey 

The pulse system consists of one Tektronix type 

162 waveform generator and three type 161 pulse generators, 

interconnected as shown in Fig. i. A type 160 A power 

supply and a type 360 indicator, used for checking pulse 

shapes, complete the system. The pulses A, B and C are 

fed into a Varian V 4311RF-unit, modified as indicated in 

• . "B" the trans- 

Figs 2 and 3 "A" is the receiver gate, 

mitter gate and "C" the 90 ° RF phase shift gate (So Meiboom 

and D. Gill, Rev. Sc. Instr. 29, 688 (1958)). 

operation: 

The pulse system has three different modes of 

i) "Time division" high resolution. The 162 

runs "recurrent" at about i000 cps. It triggers the 161 

B unit, which delivers pulses of about 20 ~sec length to 

the transmitter gate. The rising edge of these pulses 

triggers the 161A unit, which delivers negative pulses 

of about 30 ~sec to the receiver gate. In this mode unit 

161C is inoperative. 

2) T 2 measuremdnts. In this mode unit 162 is on 

"gated" and operates only when the normally closed switch S 

is pressed. Pressing S delivers a voltage step to 16i C 

and triggers a single 90 ° pulse. Unit 161B is triggered

- 2 - 

at the center of the 162 sawtooth and delivers 180 ° pulses 

at the 162 repetition rate as long as S remains open. Unit 

161A is triggered by the rising edge of the B output and 

gates the receiver. 

3) T I measurements. Unit 162 runs in "recurrent" 

mode at a low rate (period more than four times T 1 to be 

measured). Unit 161B is triggered by return of sawtooth, 

unit 161C by sawtooth after about 1/5 of period. Unit 

161A is again unchanged. Repetition rate is adjusted for 

zero signal on 90 ° pulse. 

pulse generators. 

The following modifications have been made in the 

a) In unit 161B the leads to the grids of V 5 

have been interchanged. The unit now delivers a negative 

gate rather than a negative pulse (i.e. the output is 

normally negative and goes to zero during the pulse). 

Also, the 90 ° pulse delivered by 161C is mixed with the 

180 ° pulse of 161B by connecting the cathode of V 4 B in 

the C-unit to the cathode of V 5 in the B-unit (R 33 of 

the C-unit is disconnected). 

b) In order to make for easy switching between 

different operating modes, the trigger circuits of the 

pulse units have been modified as indicated in Fig. 4. 

The two trigger modes ("negative sawtooth" and "positive 

pulse") have been provided with individual input connectors 

and individual bias potentiometers.

-3- 

c) The range of all units has been increased by 

a factor of lO, to provide for very long relaxation times. 

In unit 162 an additional position with a I0 ~F capacitor 

has been provided on SW 3. Similarly 1 ~F capacitors have 

been added to SW 2 of the 161 units.

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SPIN-ECHO MEASUREMENT OF NMR RELAXATION TIMES 

by 

R. S. Codrington 

Ridgefield Instrument Group 

Ridgefield, Connecticut 

In steady-state NMR studies the parameters of primary importance, 

apart from the signal amplitude, are the linewidth of the resonance 

and the frequency at which the resonance occurs in a given magnetic 

field. It is wel~known, however, that in order to obtain meaning- 

ful steady-state NMR spectra, the modulation frequency and sweep rate 

must meet certain conditions determined by the relaxation times T 1 

and T 2. These relaxation times, respectively called the spin-lattice 

and spin-spin times are defined by the Bloch equations. 1 In Fig. i, 

possible methods of measuring these times with steady-state equip- 

ment are shown. For both measurements, it is assumed that the steady- 

state apparatus has been set to observe the peak of the absorption 

curve. Inherent in the Bloch formulation is the assumption that when 

a sample is placed in a steady-state apparatus, the signal will in- 

crease exponentially with a characteristic time T I. The assumption 

is also made that if the r.f. driving voltage is suddenly shut off 

while a signal is being observed, the signal will decay exponentially 

with a characteristic time T2. The simple assumptions of Bloch are 

valid for NMR spectra of most liquids but they do not always apply to 

the NMR spectra of complex liquids, semi-solids and solids in which 

T2 decays with nonexponential character may be observed. The tech- 

niques of measuring T1 and T 2 described in Fig. 1 would only be use- 

ful for a restricted range of relaxation times. A direct measure- 

ment of T 1 and T 2 over a much wider range can be achieved with spin- 

echo techniques which are based on the same principles as the tech- 

niques of Fig. 1 but which utilize pulsed rather than steady-state 

apparatus. 

A great deal of information about the internal structure of materials 

can be obtained from a detailed analysis of NMR spectra. Such 

analysis usually includes studies of the linewidth or second moment 

versus temperature and the behavior of T1 versus temperature. Al- 

though in principle the steady-state apparatus can provide all the 

information required for a complete NMR analysis, it is often found 

to be easier and quicker to complement the information provided by 

the steady-state apparatus with spin-echo data. An example of the 

use of spin-echo in aiding the interpretation of steady-state NMR 

signals is given in Fig. 2. In this figure the derivative absorp- 

tion curves from two polyurethane samples are compared with the T 2 

decay curves. In the steady-state presentation, the signal from

polyurethane A is obviously narrower than the signal obtained from 

polyurethane B. However, it is noted that the signal in the wings of 

resonance A is greater than the signal in the wings of B. When the 

T 2 decays of the signals are examined, the situation becomes a little 

clearer. The straight line decay curve for polymer B indicates that 

the line shape of the steady-state signal should be pure Lorentzian. 

The faster decay of the signal from polymer A indicates that most of 

the protons in the sample are in a broad line phase. The narrow line 

observed for polymer A in the derivative steady-state presentation is 

actually only derived from about 20~ of the protons in the polymer. 

In this paper, a pulse programmer is described which is useful in 

carrying out a variety of spin-echo measurements. The unit may be 

used with r.f. pulse apparatus discussed in papers by Schwartz ~, 

Buchta et al 3, Meiboom and Gill 4, and Blume 5, and has particular 

value when used with the integrating circuits described by Holcomb 

and Norberg 6, and Blume7 Before discussing the programmer, some of 

the terms used in the spin-echo technique will be introduced briefly. 

In Fig. 3, a 90 ° pulse is defined. The term 90 ° arises from the fact 

that after the moment M 0 has been established in the d.c. magnetic 

field direction, an H 1 field is applied for a time just long enough 

to rotate the moment through 90 ° , i.e., to a position along the Y 

axis. If the HI field is intense enough, the moment will reach the Y 

axis unattenuated and in this position will induce a signal in a pick- 

up coil which will decay at an exponential rate characterized by T 2. 

If T2 is large, however, i.e., if the natural width of the resonance 

is less than the homogeneity of the magnet over the sample, the decay 

of the signal following a 90 ° pulse is determined by the magnet in- 

homogeneity. 

In Fig. 4, the echo technique, originally developed by Hahn 8, is des- 

cribed which allows the full free precession decay to be monitored in 

the presence of an inhomogeneous field. The sequence described by 

the four illustrations is as follows: a 90 ° pulse rocks the three 

magnetic moments into the direction of the Y axis. After awhile the 

moments get out of phase due to the inhomogeneity of the magnetic 

field. A 180 ° pulse, twice the length of a 90 ° pulse, is then 

applied to the system which swings the dephased moments from the 

positive Y to the negative Y direction. Moments which were lagging 

in phase are now leading in phase and vice versa. In a time equal to 

the time between the 90 ° and 180 ° pulses, the moments will come back 

into phase and form an echo signal. 

In Fig. 5a, the complete sequence is shown with the peak amplitude 

of the echo signal for all positions of the 180 ° pulse indicated by 

the dotted line. In liquids, where the diffusion constant is quite 

-2-

large, the echo signal amplitude falls off much more rapidly than 

would be the case if the decay was purely determined by T 2. The 

equation derived by Carr and Purcell for the echo signal decay is 

given in the figure. Carr and Purcell 9 were able to show that by 

applying a large number of 180 ° pulses following the 90 ° pulse, the 

echo signal amplitude could be made to follow the real T 2 decay curve. 

A Carr-Purcell sequence is given in Fig. 5b. 

Spin-echo apparatus is particularly useful in providing an easy and 

quick method of determining T I. For the T 1 measurement, a 180 ° pulse 

is first applied which rotates the moment into the negative Z direc- 

tion as shown in Fig. 6. If the apparatus is correctly tuned, no free 

precession signal should be observed following this 180 ° pulse. After 

a time Z~., a 90 ° pulse is applied and a free precession signal is 

observed which in the figure we assume to be detected with a phase- 

sensitive detector. As the time ~between the 180 ° and 90 ° pulses is 

increased, the amplitude of the free precession signal is observed to 

go to zero and then increase in the positive direction. The time qT 0 

for which the free precession signal is zero is related to T 1 by the 

expression T 1 = i~44 ~0- 

In Fig. 7, an apparatus which might be used in the observation of 

spin-echo signals is described in block form. The apparatus consists 

of a pulse programmer which provides pulses for the 90 ° and 180 ° gates 

at the times desired. The 90 ° and 180 ° gates are univibrators or one- 

shots which can be varied to produce the correct 90 ° and 180 ° gate 

widths. The two gates from the univibrators are combined in an ampli- 

fier and are used to control an r.f. gate connecting the r.f. oscil- 

lator with the sample coil assembly. The signals following the r.f. 

pulses are amplified and observed with a wide-band oscilloscope which 

can be triggered at the desired times with pulses from the programmer. 

In Fig. 8, a detailed block diagram of a spin-echo pulse programmer 

is given which can be assembled from transistorized computer logic. 

The timing of all pulses in the unit is controlled by a i00 Kc. 

crystal oscillator which drives a 6-place counter. Any time interval 

from i0 ~seconds to i0 seconds in units of i0 pseconds may be selected 

with a 6-place preset giving rise to signal G" The selected time T 

is the basic timing unit of the pulse programmer. Another 6-place 

preset (i) is used to select a time interval less than T which deter- 

mines the position of the oscilloscope trigger. Signal~drives a 

flip-flop, output Qof which is used to drive a latching pulse cir- 

cuit which produces the 90 ° pulse. The latching circuit has a 

characteristic that it lets the first pulse of Qthrough but will 

not let any subsequent pulses through until it is reset with reset 

voltage B. Signal Qon the other side of the flip-flop is used to 

(* T. J. Calvert and R. S. Codrington: To be published) 

--3--

drive both a 4-place counter and a circuit producing the 180 ° pulses. 

The number of 180 ° pulses desired can be selected with the 4-place 

preset (3). This preset drives a flip-flop which shuts off the 180 ° 

pulses until it is reset by reset B. The 4-place preset (2) is used 

to select the number of periods T after which the whole program 

sequence will repeat itself. A manual button and selector switch are 

provided so that the sequence will only repeat when the manual button 

is pushed. The 4-place preset (i) is used to select the number of 

the 90 ° or 180 ° pulse position with reference to which the scope 

trigger will be positioned. The switch showing 90 ° and 180 ° positions 

is used to select this pulse reference. A reversing switch is also 

provided so that the 90 ° and 180 ° gates may be interchanged. The gate 

widths are derived from univibrators which have both a coarse and fine 

control. 

In Fig. 9, the pulse and gate sequences at the various positions in 

the logic circuit are shown. For this particular sequence, the pro- 

grammer has been set to reset on every ten basic timing units T. A 

normal Carr-Purcell sequence has been selected with one 90 ° gate 

followed by three 180 ° gates° The scope trigger has been selected to 

be in advance of the third 90 ° pulse which actually does not occur but 

is indicated by the dotted line. The letters preceding each sequence 

refer to the positions in the block diagram of Fig. 8 at which the 

respective voltages may be observed. 

In Fig. 10, an actual oscilloscope display of a Carr-Purcell sequence 

is shown. In Fig. ii, the same sequence is presented except that the 

scope sweep amplitude has been set to display a single echo width. 

The scope trigger advance was referenced to the 90 ° pulse position 

and a value selected in terms of the clock period which would allow 

the complete echo to be displayed. Succeeding echoes in the Carr- 

Purcell sequence were then selected with the 4-place preset (i) up 

to a maximum of the number selected on 4-place preset (3) in the 

block diagram of Fig. 8. 

In addition to its use in displaying details of the echo signals, 

the flexibility of a programmer in providing a pulse at any position 

in the spin-echo sequence makes it very useful when used in conjunc- 

tion with integrating circuits for the observation of weak signals. 

-4-

References 

I. F. Bloch, Phys. Rev. 7_~0, 460 (1946). 

2. J. Schwartz, R.S.I. 2__88, 780 (Oct. 1957). 

3. J. C. Buchta, H. S. Gutowsky and D. E. Woessner, R.S.I. 2_99, 55, 

(Jan. 1958). 

4. S. Meiboom and D. Gill, R.S.I. 2_99, 688 (Aug. 1958). 

5. R. J. Blume, R.S.I. 3_22, 554 (May, 1961). 

6. D. F. Holcomb and R. E. Norberg, Phys. Rev. 9_~8, 1074 (1955). 

7. R. J. Blume, R.S.I. 3_~2, 1016 (Sept. 1961). 

8. E. L. Hahn, Phys. Rev. 8_~0, 580 (1950). 

9. H. Y. Carr and E. M. Purcell, Phys. Rev. 9_~4, 630 (1954). 

-5-

MAGNETIC RESONANCE TIMES 

OF RELAXATION EFFECTS. 

Spin- Letiice Time T~ 

Signal 

O T o T Ime 

Sample Is placed In the Ha field 

at time t • O 

Spin- Spin Time T2 

Signal ~ , 

O T 2 Time ---.- 

The R.F. field Is turned off 

time t • O 

Fiqure 1 - Steady-State Observations of T 1 and T 2 

Effects 

"S 

,'// 

J I I I 

.ioe 

I 

at 

M I Q m ~ • 

\// 

.7-" 

I I ! I 

THE 90 ° PULSE 

FigurQ 2 - Comparison of the Steady-SLate and Free Prec~aaion Signals 

Fro~ Two Polyurethanes 

i 

| 

[] 

w 

90 ° PuIN 

Fiqure 3 - The Free Precession Signal FolloWing a 90 ° Pulse 

IN ~LLlUCOMOS 

Tlml

THE SPIN-ECHO SEQUENCF 

3. 

M~ 

il 

Y 

/ \\ 

0 1 2 

90 ° Pulse 

180 =' Pulse Echo 

Figure 4 - Simplified Illustration of the Echo Sequence 

MEASUREMENT 

SINGLE 

~0 ° 

i'---to 

ECHO SEQUENCE 

(2) CARR- PURCELL SEQUENCE 

180a 2 ~._ 5~ 

• --t ¢: S e.x -f t T "tH U.& / 

2 

4. 

~-'=: ~ "- o Pl-%- I"-T'fnT " f 

1- t s Time 

Echo 

90 ° 180 ° 180 ° 180 ° 

_ I_ 2"E-I-~ Time 

Figure 5 - Single and Multiple Echo Sequences Used in the 

Measurement of T 2 

Y 

0 

X

180 ° oJO° 

Po .s'~.-- 

Ne9.~ / 

~ '~o 

MEASUREMENT 

-------M 

T, 

.I 

Null 

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SPIN-ECHO APPARATUS 

I RK OSCILLATOR 

4 

AMPLIFIER 

90" GATE 

180" GATE 

PULSE 

GENERATOR 

Figure 7 - A Block Diagram of a Spin-Echo Apparatus 

AMPLIFIER 

~OSCILLOSCOPE l

,~P//,/ EcHo Lo61c 

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0 I 7. 

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i 

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Figure i0 - An oscilloscope Presentation of the Carr-Purcell Sequence 

Figure ii - A Multiple E:[posure of the Sequence in Figure ~O with 

Only the Echo Signals Displayed

Third Conference on Experimental Aspects of NMR Spectroscopy 

Mellon Institute, Pittsburgh, Pa. 

Program of 7th Session: Broadline N-M-R Instrumentation & Operation 

Saturday, March 3, 1962,-~90-P.M. 

i¢! 

(i) "Introductory Remarks" (5 Minutes) 

Chas. W. Wilson, III 

Union Carbide Technical Center, So. Charleston, W. Va. 

(2) "Knight Shifts Observed at Low Temperatures in Crystalline Organic 

Free Radicals" (i0 Minutes) 

M. E.Anderson 

Physics Dept., North Texas State Univ., Denton, Texas 

(3) "Amplitude Calibration and Sample Preparation Work on Metals" 

(i0 Minutes) 

T. J. Rowland 

Dept. of Metallurgy, Univ. of Illinois, Urbana, Ill. 

(4) "Use of Varian V-3521 Integrator Unit with Broadline NMR" (i0 Minutes) 

Harmon Brown 

Varian Associates, Palo Alto, Calif. 

(5) "A Simple R-F Phase Detector for NMR Spectrometers" (15 Minutes) 

T. J. Flautt 

Proctor & Gamble, Miami Valley Labs, Cincinnati, Ohio 

(6) "Spectrometer Calibration, Sample Preparation, Operational Techniques, 

and New Parameters Describing Mobility in Broadline Polymer NMR 

Spectroscopy" (30 Minutes) 

W. O. Statton 

Carothers Research Lab, DuPont Experimental Station, 

Wilmington, Delaware 

(7) "TWL Probe Insert Assembly Modifications for Varian V-4340 Variable 

Temperature Accessory" (i0 Minutes) 

R. H. Elsken 

Western Utilization Research & Development Division, 

Albany, California 

(8) "A Versatile Cryostat for Magnetic Susceptibility, Anisotropy, and 

Broadline NMR" (25 Minutes) 

L. N. Mulay 

Chemistry Dept.,Univ. of Cincinnati, Ohio 

(9) Discussion of all papers.

A SIMPLE RF PHASE DETECTOR FOR NMR SPECTROMETERS 

Abstract 

A phase detector system which can be easily adapted to bridge or 

crossed coil NMR spectrometers is described. Modifications to the NMR 

spectrometer include addition of a constant impedance attenuator for 

control ~ the probe excitation voltage, a leakage control system 

independent of probe balance, and a differential dc amplifier to cancel 

changes in the leakage from spurious modulation of the transmitter 

power. 

Copies of the circuits directly applicable for a V4310 transmitter/ 

receiver unit are available at the address below. 

T. J. Flautt 

The Procter & Gamble Company 

Miami Valley Laboratories 

P. O. Box 39175 

Cincinnati 39, Ohio

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"T~L PROBE INSERT ASSEMBLY MODIFICATIONS FOR VARIAN V-4340 VARIABLE 

TEMPERATURE ACCESSORY" 

R. H. Elsken 

Western Regional Research Laboratory, l_/ Albany, California 

ABSTRACT 

In our wide-line NMRwork, we need to obtain spectra of solids prepared 

in sealed containers. For convenience of handling, these sealed con- 

tainers should also be the NMR sample tubes. 

We have modified extensively the ~.KLprobe insert for the VarianModel 

V-4340 Variable Temperature NMR Probe Accessory to accept sealed samples 

and, in t~e process, have also increased the filling factor by approxi- 

mately h. 

In brief, the supplied combination dewar probe insert and sample holders 

were discarded, and techniques suggested by S. Brownstein (Can. J. Chem., 

B7, 1119, 1939) and Paul Shafer (Mellon NMR Letters, #30, April 1961) 

w--~re followed to obtain a compatible system. As shown in the attached 

illustration, a two-component dewar and coil insert replaces the Varian 

dewar probe insert, and a 9 x 30 mm shell vial replaces the Varian sam- 

ple holder. The sample tube assembly is designed to minimize vibration 

with high gas flow rates. 

In operation, tank nitrogen flows down between the walls of the coil 

insert and dewar insert, through holes in the lower section of the coil 

insert, up past the sample tube, and out the upper end of the coil insert 

tubing. We have used this system primarily for low temperature work. 

Average stability is + 0.5 ° C when tank nitrogen flows through a con- 

stant flow regulator and copper coil -- liquid nitrogen type heat ex- 

changer. Maximum flow rate is approximately 16 liters per minute for 

-195 ° C sample temperature. 

~/A laboratory of the Western Utilization Research and Development 

Division, Agric itural Research Service, U. S. Department of Agriculture. 

Reference to a company or product by name does not imply approval or recam- 

mendation of the product by the Department of Agriculture to the exclusion 

of others which may also be suitable.

F 

Z- 3 MM TUBE 

,.,, PROJECTS THRU 

,: ~! 

HOUSING 

' '~;":~~HOLD DOW-'~-~-N 

JMODIFIEO 

TWL VARIABLE TEMPERATURE 

" : 2 ~ ' f f 

, :,~.~ ~,RIAN_/ 

;..~,~:~.. DEWAR INSERT 

,:~,:~,,;:,'~ :" ~MATCHING CAP 

_J ASSEMBLY~ 

TC LEADS 

ADAPTER RING 

.3 MM O.[).~ 

GLASS TUBING INSERT HOLDER 

(TEFLON)" 

~[ CORK SEAI ~ 

Ox30 MM 

SHELL VIAL 

q 

GLASS ROD 

ION SHELL VIAL 

:OIL INSERT 

TC LEADS 

SNUG FIT ON 

3 MM TUBING| 

PROBE ADAPTER 

HOUSING 

NITROGEN 

m m~m 90 

)EWAR INSERT 

A 

EXIT NITROGEN 

i COIL INSERT 121) mm 

DETAILS 

I ' 

TEFLON BNC 

SPACER CONNECTOR 

t 

II mm 

Iq mm 

BOTTOM 

INSERT SEAL 

(TEFLON) "'"~ ~:~t-~ mm 

~ UG FIT ON 'LL___:J--v- 

C01L INSERT

Third Annual Conference on the Experimental Aspects of N-~-R 

Spectroscopy Session on Broadline N-M-R Operation and 

Instrum6n ration 

L. N. Mulay 

Magnetochemistry Laboratory, Department of Chemistry 

University of Cincinnati, Cincinnati 21, Ohio 

Abstract of Paper 

A Versatile Cryostat for Magnetic Susceptibility, Anisotr~py 

Broad Line N.M.R. 

A versatile cryostat for magnetic susceptibility, anistropy 

and Broad-line N.M.R. work has been constructed. It utilises 

the Dewar vessels with ground-joints at the lower stem as described 

previously by the author (Rev.Sci. Instrum. 28, 279,1957). The 

principle used for maintaining a given temperature is different 

from that described in this paper. The volume enclosing the 

sample is heated electrically with a non-inductive coil. This 

is surrounded by liquid nitrogen through appropriate glass- 

wool insulation. The particular design permits uniform tempera- 

tures over as large a distance as 15 cm. which is particularly 

useful for the Gouy technique, which uses long sample tubes. It 

may be noted that the older technique of simultaneous heating 

and cooling of a metal block, surrounding thc sample produces 

appreciable heat gradient over such a long distance. 

Using liquid nitrogen, temperatures between -196 ° to 25°0 

(Room Temperature) are easily obtained, with a minimum loss at 

the high temperatures. However, for economy in the use of liquid 

nitrogen above -80°0 one may use dry-ice acetone. (This interferes 

with proton magnetic resonance studies. Hence, in this case one 

may use carbon-tetrachloride and dry-ice mixture for obtaining 

temperatures well below room temperature.) With no coolant, 

temperatures as high as 250°C may be obtained easily. In this 

range no heat is allowed to leak to the pole faces of the magnet, 

which remain protected at+all times. It has been possible to maintain 

temperatures within-I °c without any special regulating 

devices However, by u 

sing ele 

-~ 

ironic 

. 

circuts, 

A 

it 

of 

is 

advantaged 

possible 

of 

to maintain temperatures within O.I°C number 

this cryostat will be discussed. The information is scheduled to 

appear shortly in the literature.

A. 

B. 

GS : jmw 

2127162 

T.C.O.E.A. 0. N.M.R.S. 

8th Session: March 3, 1962, 2:00 P.M. 

Catalog of NMR Spectral Data 

1. G. Slomp: IBM Coding of Shift Data (5 min. ). 

2. LeRoy Johnson: The Varian Shift Catalog (20 min. ). 

3. Ernst Lustig: Proposal for an Indexed Timely NMR Bibliography 

(5 min. ). Discussion of Proposal (10 min. ). 

Spectral Analysis 

1. Aksel Bothner-By: Introduction and Discussion of Various 

Computer Techniques (35 min. ). 

2. Ernst Lustig: Comments on Swalens 8-Spin Program for IBM-7090 

(5 min. ). 

3. Dan Elleman: Comments on Their Results and on the Use of Spin 

Decoupler to Determine Signs of Coupling Constants (15 min. ). 

4. J. Baldeschwieler: Comments on Their Program, Analysis of Double- 

Resonance Spectra~ Higher Spins and Larger Shifts (15 min. ). 

5. Other Comments and Discussion (i0 rain. ).

_ _ . y~...-.'.: 

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MAIN GROUPS 

FUNCTIONAL GROUPS 

1. R---CH 3 a. "--CH 3 

2. R--CH2--R' b. ---CH2-- 

I 

3. R--CH--R" c. ---CH-- 

I I 

R' d. --C-- 

4. R--CH=N--R' I 

5. R---CH=CHz 

6. H~C__C~ R' 

R I ~H 

e. --CI 

f, --F 

cJ. --Br 

h. --H 

H~ c C ~H 

7. = i. --I 

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R~ ~H 

8. R~C'--C~H k. --C ~O 

9. R'~'C=cIR" I. --C= 

R I ~H I 

10. R--C~CH m. --N-- 

11. 

110 

R---C~H 

n. --N~ 

o. --O--or--> 0 

1 2. R~//O p. --OH 

~OH 

q. --O---C~ ° 

13. R--OH 

14. Phenyl 

15. Pyridyl 

16. Furanyl 

r. --NOz 

S. --S~ 

t. --C=C-- 

17. Pyrryl u. ~ N 

18. Thiophenyl v. Phenyl 

19. Misc. aromatic w. Aromatic ring junction 

20. R'~NH 

x. Misc. aromatic 

R ~ y. Thiophenyl 

21. H on other atoms z. Misc. atom

I 

2 

301,302 ! 

. . . . . . ;. ~. . . . . . . . . ; . + , , . . . . - t + + - * * ~ ÷-J *++~ . . . . . . *-+++ - "-;-$*' ' , . . . . . 1 1 + . + . , . F . . . . . . + - f - , - * . . . . . . t .... 

. . . . . . . . . . . . . . TT:i:-~T, "Ti .-~nTII~-~-TT. --7 T~ :. .... ~ i, IL +T-T:I -T- 

..... = = ...... = ...... = 

. . . . . . . . . . + . . . . . . . . . +. + + . . . . . 

. . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . ~ ...... I1" "-+f ........ T-,Ji" " : I-L'.LLL~+E.]L_~_]_::-L _--. 

-~ .... 1 .................. +-tT+ITT 7''T+tTi t-+TTT ilL]_ - - _T. ;]:,. -L$- -r. :.$~t____iL:--.. -- --. 

:----L--Z--~--.~.+--$.LL --" .'LL.;L::+;;.++ ;-i;.--ii.'.+ ;U .... ' . . . . . . +.l-+.- ................... 

, , I , , , , i , , , , I . . . . , . . . . I . . . . i . . . . I , , , , J , , , L I L L * i . . . . I . . . . i , , , , I . . . . i . . . . I . . . . I . . . . i , , , 

8.0 7.0 6.0 5.0 4.0 3.0 2.0 1.0 0 PPM 

301 

I - met hyl -4- (2-pyridyl) piperidine - 

CF~I-~eN20 ~ 4-corboxylic ocid methyl ester 

II (b) 

(f) [/.~C -- 0 M e 

~N" 

I 

(a) Me ~ss,~.~..,,s 

Sweep offset: ~,D_ ppm a ~ e J~6-4~_ 

Freq. response: __Leps b__3..~_9 f J,5_4 

Sweep time: __5.0_0_ sec c ~.J_4__ g __.'7~..O]g~. 

Spec. amp: __1.2,5__ d 7.34 h 

i 

302 

• ,,,,===, Procoine 

C,~HmN202 

(f) (g) 

(b) (o) 

H/~.~H i01 (e) (c) / Hz--CH~, 

(d) HzN'-- ~ ~-- C-- O-- C H2--CH~-N \ 

H~-~-~H CH2"-CH 3 

(f) (g) (b) (o) 

3 ~ ~11; N :,~ F ;11 & 

Sweep offset:~-- ppm a ~ e ~ 3 _ L 

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I ' ~ I T ? I I T I f I I I I I ' ' ' ' ' ' ' ' ' I 

• ,6o; "-TT ".:, : ~'-4&o - ~ 3oo . . . . . . . zoo . . . . . . oo . . . . . 9cPs I 

2~) '* . . . . + . . . . . . . . . * . . . . . . . - *'~- . . . . . . . . . . . . # I 

leo + • . . . . • + . . . . . . . . . ' . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . . 

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zOO 

50 

400 

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303 

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p-phenyl phenocetyl bromide 

(b) (c) 

H H 

H H 

(c) (c) 

C. (el 

\CH 2- 

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Spec. amp: __ 16 _ d _ _ h_ _ 

I000 

, . . i . . . . i , . . r I . . . . i , . t . . . . f . . . . 1 • 

Br 

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304 

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50 

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g 

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3

0 

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o 

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< < .:: .= .:: < ~ = ~ = = = = : =~=o 

0 

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A 

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o _- - m

ANALYSIS OF HIGH-.RESOLUTION 

NMR SPECTRA BY THE ITERATIVE METHODS 

by 

S. L. Manatt and D. D. Elleman 

Physical Sciences Division 

Jet Propulsion Laboratory 

California Institute of Technology 

Pasadena, California 

In this handout explicit expressions are given for the pertur- 

bation of the energies levels of the ABC and A2B 2 NMR systems as derived 

from the perturbation treatment of Hoffman 1~2 for the analysis of high- 

i. R. A. Hoffman and S. Gronowitz, Arkiv Kemi l_~, 45 (1999). 

2. R. A. Hoffman, J. Chem. Phys. 32, 1296 (1960). 

resolution spectra. From the energy levels it is possible to obtain the 

perturbation expressions for all the transitions. 

tonian into 

This perturbation method starts by decomposing the NMR-Hsmil- 

° 

H = H(°)+H (I) 

where = H ( tA)~ ~ 9 • • ? ~ ~) • • °• ) is the approximate 

Hamiltonian derived from a first guess of the NMR parameters. Ways of 

obtaining this first guess are well known. If the ~2~ and ~j of 

the guess are good approxlmations to the quantities ~£ and ~[~ then 

H (°) nearly equals H, and H (I) may be treated as a perturbation. By 

transposing H (O) we get: 

H - H (1).

First-order perturbation theory gives for the energy level number ~ !, 

L ~ . Thus the first-order corrections 

to the transitions energies are given by the differences of the form 

• 

Below the results for the ABC system~it is hoped~are given in 

sufficient detail to be understandable. The results for the ABC and 

A2B 2 systems were derived by us sometime ago, but they have not been 

exhaustively checked for algebraic errors. We present them here for what 

they are worth to the practicing NMR spectroscopist. We have also 

obtained the perturbation expressions for the transitions of the ABC and 

A2~ systems which are easily derivable from the energy level perturbations 

given here. We have similar results for the ABX, A2X2J ABC B and ABX 3 

systems. We hope to make this work generally available soon either as a 

JPL report or external publication. 

2

T~ A 5 C S yst:'~ 

) 

State ~.~a q, s P1atr~ Eie~e~% 

A~c 

I0,.= oI, ~(~ 

Z 

Z 

30,, _± +i _ 

H**- ~.(-%+%+~,~) ~.(Y^~-T~O&,.) 

"Z ~ 

2 o,,_ I~,(; 

Z 

"3&i 

-- (~~ 

~. .. 

H7.4 = -~T~ -'Tac 

,~.- -~ ~-~ H~.~ = -k &~ 

: |

]'h ~s iTh~s 

II 

is &cc~f,t~sh~_J. by ±~e ¢i~enwct~- 

Cii 

¢"¢z Co~, C~ 

l..J 

C-~5 C~,o~, C.,,,_ 7

• 

a.

~! 0 V,,' W e._. ~ "&.Ve.. 

H m _ H -H ° 

e, am pl e camSiaee 

= c;~ (.~ I,-~°1~)~ - C43 

"~ o._ u o t o " 

X 

%*%-~- ~(%-r, io)-'- '~ ~°

C o l i e c~t , n ~ ' -t_ e ~- ,',-,'-, o ~ ~ In ~x ~, ., 

H Ol - ~ r-. z . z z 

-c.~]L%- 

~E- , z 

~F.C2 C z _7. 

(.. 

{.,. 

E! " 

-tl~c 

~ --~ c~ ~ %., ~e + ..~c~ a %~ ~, ( ~qc,,). 

~"t, ~ • 

w~e)-c 4C _ ~ . .-z -z 

e_~; ~)re 5S i eva 

I 

Z 

• --- j5

C-" -"~ ~ ~ ." - ~e ~-~ -'~ ~3 "-~ ~ ~- • 

~ ~, .~-4- .,. '~ ÷ .~, I ~ % .% + 

'~ 4- --t- .j .._, ~ ~ ~,,t: .~ ~'~ R ,4:. :~ 9 

..~ ~ I.~ < .~ .~ ~ ,< ---, r-:. :~ < ~" ~ "-:', ,~ 

.2 -4- "=. ."' ,,3 "J- • ~ •, ~ ~"" .~ ~- 

~' ,.0 '~ t~

S z 

IS I 

'ZS~ 

ISo 

"35o 

clS~ 

IS 

-'I 

2~_i 

It~ I 

I~. o 

I& -I 

?--o,, -I 

N : 

T^~+~-^~ 

AA~ 

o~A o(o{ 

~ ~-~ ¢~-~,~I 

/"h~ 

, . ~(~,~) 

I 

AT. Bz 

_ l H,,- -~I~ 

14 .z~ = - £i ~ 

H ---cu- 

N~- -~ 

14-I~ = 0 

H -- i 

qc I -- --~t~ 

,. --iN 

Ii-- 

H~= i~,-~ ~,~M 

bl ~,E = 0 

I 

~N 

M-:r,A-~ ~A_~o = 

_i 

H¢-I=--Iw

t4,t 

l'i' Z. z . I"lg,.-j 

I'1~,. t kt~,s-H,s.. ~. i4~ 

1~7'fl- H"7~ H-,-.//= H-77 H 

II Hi~. 

all2. I ~1"~.2 ./. 

GT~ C,-/~. 7L, C.7 7 

mhe~e ~e $~e 

"He¢~j4~ 

cq~ C~q 

,(-:-; y ~;~ e m ~ e_t-. : 

I-lot< ~ 

~1 i('l~i, z 

~...Z i('i~ 2.. 2 

~f_ %,

I ! 

(t ~ He°If = .-~ 

~ The A z~3 z S'×st.e.~ 

i " "7- "7. • 

I~% i,~'l ~%) --_-~:,4Cc,~.~)~ ~ + c,.,c....c._c _, ~ 

• C%,t 

C~i ~) I'~%') = - ( clcc~ ) au, +[cu% + c:.~q. ~-k(c~.+c~_)]a~, + 

[C~4.c~. ~ i- %.~Cc. C c~c~...~ ) a~ - c~. 7- a 

(,~;i .~'I,~) = -(~ _c?,a~ ~ ~[c~c.~q~q

THIRD CO~."FERENCE ON EXPERIMENTAL ASPECTS OF N.M.R. SPECTROSCOPY 

Harry Agahigian 

Olin Mathieson 

275 Winchester Ave. 

New Haven, Conn. 

A. Louis Allred 

Northwestern University 

Evanston, Ill. 

Ernest W. Anderson 

Bell Telephone Labs. 

Murray Hill, N. J. 

Mary M. Anderson 

Hercules Powder Co. 

Research Center 

Wilmington, Del. 

WestonAnderson 

Varian Associates 

611 Hansen Way 

Palo Alto, Calif. 

F.A.L. Anet 

Dept. of Chemistry 

University of Ottawa 

Ottawa, Ontario 

Canada 

N. C. Am6elotti 

Dow Coming Corp. 

Midland, Michigan 

MELLON INSTITUTE, PITTSBURGH, Pennsylvania 

MARCH 2 and 3, 

ATTENDEES 

James Bacon 

McMaster University 

Hamilton, Ontario 

Canada 

A. W. Baker 

The Dow Chemical Co. 

Western Division 

Pittsburg, Calif. 

John D. Baldeschwieler 

Chemistry Dept. 

Harvard University 

Cambridge , Mass. 

~upert D. Barefoot 

Naval Propellant Plant 

Indian Head, Md. 

Richard C. Barras 

Atlantic Refining Co. 

Philadelphia, Pa. 

William F. Beach 

Union Carbide Plastics Co. 

Bound Brook, N. J. 

Edwin D. Becker 

National Institute of Health 

Bethesda, Md. 

Paul Bender 

Univers~of Wisconsin 

Madison, Wisc.

Thomas E. Beukelman 

E. I. duPont De Nemours 


T. Birchall 

McMaster University 

Hamilton, Ontario 

Canada 

Robert B. Bradley 

National Institute of Health 

Bethesda, Md. 

Edward G. Bram____~e, Jr. 

Polychemical Dept. 

E. I. duPont de Nemours 


z. Z. Bray 

Socony Mobil OilCo. 

Dallas, Texas 

Wallace S. Brey, Jr. 

University of Florida 

Galnesville, Fla. 

Harmon Brown_ 


611 Hensen Way 


G. L. Buc 

Fisher Scientific Co. 

711 Forbes Avenue 

Pittsburgh, Pa. 

Kenneth Bucher 

~ Wm. Ritchey 

Standard Oil Co. of Ohio 

Cleveland, Ohio 

John J. Burke 

Mellon Institute 


John W. Caftan, Jr. 

Pennsylvania State University 

~niversity Park, Pa. 

Donald G. Davis 

Carnegie !ns.Tech. 

Pittsburgh 13,Pa. 

Hung Yu Chen 

U. S. i. Chemicals 

Cincinnati 37, Ohio 

L. D. Colebrook 

Department of Chemistry 

University of Rochester 

Rochester, N ° Y. 

Charles M. Combs 

Eastman Kodak Co. 

847 Jaclyn Lane 

Webster, N. Y. 

Charles Constantin 

Texaco, Inc. 

P. O. Box 509 

Beacon, N. Y. 

James L. Dennis 

Marbon Chemic~ Div. 

Borg-Warner Corp.. 

Washington, W. Va. 

F. E. Dickson 



Dean C. Douglass 


Murray Bill, NI J. 

Gerald Dudek 


Harvard University 

Cambridge, Mass. 

Ralph R. Eckstein 

Monsanto Research Corp. 

Mound Laboratory 

Miamisburg, Ohio 

Daniel D. Elleman 

Jet Propulsion Lab. 

Calif. Institute of Tech. 

Pasadena, Calif.

R. H. Elsken 

U.S. Dept. of Agriculture 

Albany, Calif. 

Raymond Ettinger 

Rohm & Haas Co. 

Huntsville, Ala. 

Burton P. Fabricand 

Columbia University 

Hudson Labs. 

Dobbs Ferry, New York 

Harry D. Fair, Jr. 

Picatinny Arsenal 

Dover, N. J. 

Raymond C. Ferguson 

E. I. duPont Exper. Station 


George Filipovich 

Minnesota Mining & Mfg. Co. 

St. Paul, Minn. 

Harold Finegold 

Nat'l Bureau of Standards 

Washington 25, D. C. 

Pat. W. Flanagan 

Continental Oil Co. 

Ponca City, Oklahoma 

T. J. Flautt 

Procter & Gamble 

Miami Valley Labs. 


G. Fraenkel 

Ohio State University 

88 W. 18th St. 

Columbus, Ohio 

Anthony Fratiello 


Murray Hill, N. J. 

R. A. Friedel 

U. S. Bureau of Mines 

Pittsburgh 13, Pa. 

John Gergel~ 

Retina Foundation 

Mass. General Hospital 

Boston, Mass. 

David M. Grant 

University of Utah 

Salt Lake City, Utah 

Robert L. Griffith 

Eastman Kodak Co. 

Rochester, N. Y. 

Herbert Grossman 

Sohio Research 

4440 Warrensville Cntr. Rd. 

Warrensville Heights, Ohio 

Henry Gruen 

U.S. Bureau of Mines 

~800 Forbes Avenue 


Mack C. Harvey 

E1 Paso Natural Gas Prod. Co. 

E1 Paso, Texas 

W. J. Hawley 

University of Pennsylvania 


Jerry Heeschen 

The Dow Chemical Co. 

Midland, Michigan_ 

Maurice A. Henry 


Whitmore Lab. 

University Park, Pa. 

Leslie A. Heredy 

Carnegie Institute of Tech. 


John J. Hill 

Department of Physics 

St. Louis University 

St. Louis, Mo.

James C. Hindman 

Argonne National Lab. 

Argonne, illinois 

Robert Hirst 

University of Utah 

Salt Lake City 12, Utah 

Donald P..Hollis 

VarianAssociates 



Daniel H~ndman 

American Viscose Corp. 

Marcus Hook, Pa. 

Francis L. Jackson 

Rohm & Haas Co. 


Morton H. Jacobs 

Int'l Flavors & Fragrances 

Rose Lane 

Union Beach, N, J. 

L. F. Johnson 




Robert C. Jones 




J. A. E. Kail 

Osmond Lab. 

Pennsylvania State Univ. 

University Park, Penna. 

R. W. King 

Iowa State University 

Ames, Iowa 

Harold Klapper 

Chemical Warfare Labs. 

Army Chemical Center, Md. 

Lawrency J. Kuhns 

Callery Chemical Co. 

Callery, Pa. 

R. U. Kurland 

Carnegie Institute of Tech. 


Paul W. Landis 

Eli Lilly & Co. 

Indianapolis 6, Indiana 

Paul C. Lauterbur 

Mellon institute 


Wallace C. Lawrence 

Chemstrand Research Center 

Durham, N. C. 

Nerms~ Li 

Duquesne University 

Pittsburgh 19, Penna. 

Wayne Lockhart 




Ernest Lustig 

Nat'l Bureau of Standards 

Washihgton 25, D. C. 

J. ~.= LuValle 

Fairchild Camera & inst. Corp. 

500 Robbins Lane 

Syosset, N ~. Y. 

David W. McCall 

Bell Telephone Labs 

Murray Hill, N~ J. 

Neal L. McNiven 

Worcester Foundation 

Shrewsbury, Mass. 

Edmund R. Malinowski 

Stevens Institute of Tech. 


Hoboken, N~ J.

Dale ~. 

.all e~.~ _y Chemical Co 

Callery, Pa. 

Stanley L. Manatt 

Jet Propulsion L~o. 

Calif. institute of Tech. 

Pasadena, Calif. 

Nichard W. Mattoon 

Abbott Laboratories 

Physical Chemistry Dept. 

North Chicago, Ill. 

David G. Mehrtens 

E. i. duPont de Nemours & Co. 

Benger Lab. 

Waynesboro, Va. 

S. Meiboom 


Murr_ay Hill, N? J. 

M. T. Melchior 

Esso Research & Devel. 

Linden, N. J. 

Pr~_uk W. Me!po!der 

Atlantic Refining Co. 


james F. Miller 

Continental Can Co. 

7622 S. Racine Ave. 

Chicago 20, ill. 

George F. Mi!liman 

Carnegie institute of Tech. 

Pittsburgh i3, Pa. 

Daniel A. Montalvo 

Southwest Research Institute 

San Antonio 6, Texas 

john ~. Moran 

I___an Associates 

6]_1 H~nsen Way 

Palo A±~o, ''~ Calif. 

L. N. Mulay 

Univ. of Cincinnati 


Cecile Naar-Colin 


New Haven 4, Conn. 

Maria Teresa Neglia 

American Cyanamid Co. 

Stamford, Conn. 

Forrest Nelson 



PaloAlto, Calif. 

Peter H. i'liklaus 

S~,~OZ, S,~it zerland 

Thomas F. Pag___~e, Jr. 

Battelle Memorial Institute 

505 King Ave. 

Columbus, Ohio 

H. W. Patton 

Tennessee Eastman Co. 

Kingsport, Te~m. 

Edward O. Paul 

University ofb'tah 

Salt Lake ~t" ~. y 2, Utah 

Alexander Penchuk 

Hs-~vard Medical School 

Dept. of Pharmacolo~ 

Boston, Mass. 

J. A. Pople 



Elton Price 

%~itemore Laboratory 


University o~ .... , Penna. 

Herbert L. Retcofsky 

U. S. Bureau of Mines 

hSOO Forbes Avenue 

Pittsburgh l~, Pa.

John G. Rickert 

Mellon institute 


Ti!im~nn A. Richter 

Picatinny Arsenal 

~c, ver, :~. --o j. 

Wi!!iam:M. Ritchey 

Standard Oil Co. of Ohio 

C!evei~nd ~o, -~ Ohio 

Mark Rycheck 



David i. Schuster 

New iork UniversSty 

~ew ~ork , N. Y. 

Miles Schwartz 

Vari~n Associates 

611 H~nsen ~.iay 


Paul R. Sharer 

Dartmouth College 

H~noverj !~. n. 

5. C. Shapiro 

5[elion institute 

Pittsburgh i5, Pa. 

A. G. Sharkey~ jr. 

U. S. ~ureau of Mines 

Pittsburzh 13, Pa. 

J? i,[. Shoo!ery 

Vari~_nAssociates 

611 H~nsen Way 

Pa!o Alto, Calif. 

Wilbur Simon 

Universal Oil Products Co. 

Des P!aines, iii. 

Hertha Skaia 

UniversaiD-fT Products Co. 

Des Plaines, Ill. 

George Slom_____2__D 

The Upjohn Co. 

Kalamazoo, Mich. 

W. O. Statton 

E. i. duPont de Nemours Co. 

Experimental Station 

Wilmington, De!. 

Burch B. Stewart 

Allied Chemical Corp. 

Morristc~m, N. J. 

J. B. Stothers 


University of Weste.~n Ontario 

London, Cntario 

Canada 

A! Svi_-mickas 

Argot_he Nat'i Lab. 

Argonne, !!i. 

A. Taurins 

McGili University 

Montreal, Canada 

G. Tiers 

Minnesota Mining & Kfg. Co. 

St. Paul 19, Mi~m.. 

David M. Vea 


Springfield, N. J. 

G. D. Vickers 


New Haven, Conn. 

Martin~ 

Rutgers University 

New Brunswick, N? J. 

J. C. Westfahi 

B. ?. Goodrich Research Center 

Brecksviiie, Ohio

Kermit W~etsel 

Tennessee Eastman Co. 

Kingsport, Tenn. 

Horace F. ~ite 

Research Dept. 

Union Carbide Chem. Co. 

So. Charleston, W. Va. 

T. K. Wiewiorowski 

Freeport Sulphur Co. 

Po~ Nickel, La. 

R. E. Wiifong 

E. i. d~ont de Nemours & Co. 

Wilmington, De!. 

Charles W. Wilson i!I 

Research & Development Dept. 

Union Carbide Chemical_Is Co. 

So. Charleston 3, W. Va. 

Nancy Wilson 


Pittsburgh !5, Pa. 

William B. Wise 


Department of Chemistry 

james C. Woodbrey 

Mons~nzo Chemical Co. 

Plastics Div. 

Springfield 2, Mass. 

Paul j. Yajko 

f'.M.R. Specialties 

505 ~!ngston Dr. 


JohnT. Yoder 

Monssmto Chemical Co. 

inorganic Research 

St. Louis 66, Mo.

rd  - 1962 - ENC Conference

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