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"" 314 MRB4oo6-Q6

RESEARCH ON ORGANIC DEPOLARIZERS

Report No. 6Contract No. DA36-039-SC-87336

DA Project No. 3A-99-09-002

Sixth Quarterly Progress ReportS1 October 1962 to 31 December 1962

* U. S. Army Electronics Research and DevelopmentPort. LaboratoryFort Monmouth, New Jersey

MONSANTO RESEARCH CORPORATIONBOSTON LABORATORIES

EVERETT 49, MASSACHUSETTS

* .:

"TDiA

NQ'.-QTh

ASTIA AVAILABILITY

Qualified requestors may obtain copies ofthis report from ASTIA. ASTIA release toOTS not authorized.

MRB4oo6Q6

RESEARCH ON ORGANIC DEPOLARIZERS

Report No. 6Contract No. DA36-039-SC-87336

DA Project No. 3A-99-09-002

Sixth Quarterly Progress Report1 October 1962 to 31 December 1962

OBJECT

The object of this work is to develop new organic compounds andsystems that will lead to organic-depolarized primary cells withhigher voltages and capacities than the present Mg/MgBr 2 /m-DNBsystems (m-DNB will be used throughout as an abbreviation form-dinitrobenzene). Any new system so developed should have theflat discharge and high capacity of the Mg/MgBr 2 /m-DNB cell.

Authors

Bernard A. GruberElizabeth A. McElhill

MONSANTO RESEARCH CORPORATIONBOSTON LABORATORIES

EVERETT 49, MASSACHUSETTS

I

I TABLE OF CONTENTS

Page No.

I. PURPOSE .................................................. 1

II. ABSTRACT ................................................. 1

III. SUMMARY AND CONCLUSIONS .................................. 1

I IV. RESULTS AND DISCUSSION ................................... 2

A. Correlation of Half-Cell Data with Chemical Structure 2B. Experimental Procedure................................. 7C. Half-Cell Tests ...................................... 8

1. Halogen Addition Compounds ..................... 82. Aromatic Nitro Compounds ....................... 93. Trinitro-P-naphthoic Acids ..................... 134. 1,3,6,8-Tetranitrocarbazole .................... 135. 4-Nitroimidazole............................... 136. Sodium Salt of Nitranilic Acid ................. 147. N,N'-(1,2-Ethylene)bis maleamic Acid ........... 148. Phosphomolybdic Acid ........................... 149. Peroxides ...................................... 1510. m-Dinitrobenzene in Electrolyte with Added

Methanol ..................................... 1511. Ferrocene ....................................... 1512. Depolarizer Mixtures ........................... 1613. Leuconic Acid .................................. 17

D. Stability of Halogen Addition Compounds in DryStorage and in Electrolyte ........................... 18

I E. Corrosion Tests ...................................... 18

F. References ........................................... 19

V. PROGRAM FOR NEXT QUARTER ................................. 19

I VI. CONFERENCES ............................................... 21

VII. IDENTIFICATION OF PERSONNEL.-.............................. 21

I VIII. APPENDIX .................................................. 135

A. Methods Used for Preparation of Compounds Tested ..... 135

1. Halogen Addition Compounds ...................... 1352. Leuconic Acid ................................... 13913. Salts of Acids .................................. 1394. Trinitro-p-Naphthoic Acids ...................... 139

I IX. REFERENCES ............................................... 139

I

I

I. PURPOSE

The purpose of this work is to develop new organic compounds andsystems that will lead to organic-depolarized primary cells withhigher voltages and capacities than the present Mg/MgBr 2 /m-DNBsystems (m-DNB will be used throughout as an abbreviation for m-dinitrobejnzene). Any new system so developed should have the flatdischarge and high capacity of the Mg/MgBr 2 /m-DNB cell.

I II. ABSTRACT

Half-cell measurements on all depolarizers tested during the con-tract have been tabulated. From these data, depolarizers meetingcertain specifications were segregated.

No consistent quantitative correlations were found between half-cell characteristics and the electronic strengths of substituentson nitrobenzenes or on other type depolarizers. The magnitude ofthe electronic effects of substituents on depolarizer activity isdiscussed and half-cell characteristics are compared to polaro-graphic data from the literature.

Stable halogen addition compounds of heterohalides and of chlorinewere prepared and tested. Various halogen addition compounds withthe structure -NHXX 2 have proved stable in dry storage and inelectrolyte for extended periods.

Inhibition of corrosion of magnesium by tetrasodium dinitropyro-mellitate and other similar soluble nitro compounds was confirmedj by extended corrosion tests.

A slight increase in reduction efficiency of bnnzoquinone wasrealized in benzoquinone o-DNB mixes. Methanol (10 and 25% concen-tration) in ammonium bromide electrolyte lowered the reductionefficiency of m-DNB.

I III. SUMMARY AND CONCLUSIONS

Half-cell measurements on all depolarizers tested so far weretabulated and the data analysed in an effort to correlate half-cell characteristics with chemical structure. The various half-cell characteristics such as open circuit potential, coulombicefficiency, and average operating potential were found to give noconsistent quantitative correlation with the electronic strengthsof substituents. A review of polarographic data in the literaturewas made to determine the relationship of the electronic strengths ofsubstituents to half-wave potentials. Several series of reductionswere found that gave quantitative correlation (pH dependent). Themagnitude of the effect of substituents on half wave potential wasfound to be small. Thus, these electronic substituent effects areovershadowed in half cell tests where physical effects (such assolubility and absorbency on carbon are large.

!1

Tests with halogen addition compounds were extended to obtain com-pounds with higher capacities ani good storage stability. Compoundswith the structure )NHXX 2 were the most stable and compounds suchas quinolinium chloride perbromide were stable for a month both inelectrolyte and in dry storage. A stable perchloride, quinoliniumiodide perchloride, was also found. Stable heterohalide compoundssuch as quinolinium chloride iodine trichloride, trimethylammoniumchloride iodine bromide, etc. were found to reduce with highefficiencies but with greater polarization than the perbromides.Additional tests at high drain rates with quinolinium chlorideperbromide confirmed earlier tests by demonstrating its very lowpolarization at high drain rates (0.4 amp/g or 1.0 amp/in2).

The inhibition of corrosion of AZ-10 magnesium cans by tetrasodiumdinitropyromellitate was confirmed by extended corrosion tests.Other soluble nitro compounds were also found to be effectiveinhibitors. Inhibition was effective both in the presence andabsence of chromate inhibitors.

Two systems involving a combination of electrochemical reductionsand chemical reaction of components in a depolarizer mixture weretested. In the first, o-DNB mixed with benzoquinone was found togive a slight improvement in the capacity of benzoquinone by aregeneration reaction. In the second system, sulfides added toiodine proved ineffective in increasing the reduction potential ofiodine.

The efficiency of reduction of m-DNB was lowered by the additionof methanol to the electrolyte. The lowering was probably causedby reduction of absorbency of m-DNB on the carbon in the presenceof methanol.

Screening tests with peroxides were continued. Peroxides testedthus far have polarized badly at low current drain.

IV. RESULTS AND DISCUSSION

A. CORRELATION OF HALF-CELL DATA WITH CHEMICAL STRUCTURE

Correlation of depolarizer activity with chemical structure fallsinto two groups: first, correlation with the structure of the activegroup, and second, correlation of the effect of added substituentson activity of a given reactive group. The first correlation requiresan involved quantum mechanical treatment and has not been attempted.Empirically, it can be seen that depolarizers reducing at highpotentials generally have structures where a relatively weak bond isbroken on reduction (e.g. halogens) and poor depolarizers havestructures where a relatively strong bond is broken (e.g. -CZC-).However, bond energy of the reactive group is not the only importantfactor in half cell performance since no correlation of bond energieswith cell characteristics of depolarizers has been found. Indeed,some mechanisms of reduction may involve bond formation as the acti-vation step.

There is a vast background of work on the effect of substituents onchemical reactivity. However, thermodynamic data are scanty. Themagnitude of the effect of substituents on the theoretical reductionpotential of a depolarizer can be calculated from the free energiesof formation of reactants and products. Experimental values of freeenergy of formation for o-DNB, m-DNB, o-nitroaniline and m-nitro-aniline are given by Parks and Huffman-(Ref. 1).

,<N..NH 2

,. ,N02 + 6 - + 4H20 1 2 + 6oH-'-N02 -N0 2

1 49,400 cal 41,400 cal

02+ 6 + 4H20 N0 + 60H-

NO02 QH 2

42,900 cal 4o,4oo cal

The difference in free energy for the reactions are:

LFO ortho = (49,400 - 41,4oo) +.4- F° (H20) -64 F° (OH-)

AF° meta = (42,900 - 40,400) + 4AF° (H20) -6LF° (OH-)

f/kAF° = 8000 - 2500 = 5500 cal

Therefore, the increase in reduction potential, Eo, that can beexpected for reduction of o-DNB compar-ed to m-DNB is 5500/6(23,060) =0.0398 volt.

This is a very small increase in potential although the nitro groupis one of the strongest electron-withdrawing substituents when in theortho (or para) position. The low value indicates that only minorchanges in theoretical reduction potential can be expected fromsubstitution effects.

However, the reduction potentials of most depolarizers are limitedkinetically where substituent effects may be more important. Polaro-graphic measurements (e.g. half-wave potentials) illustrate the magni-tude of effect of substituents on depolarizer groups since suchmeasurements are not complicated by the physical variables thatinfluence half-cell discharge measurements. Polarographic data forsubstituted nitrobenzenes (Ref. 2) show that the magnitude of theeffect of substituents on reduction potential is dependent upon pH:

pH 1 H 3 pH 6 pH 10E (vs. S.C.E.) Nitrobenzene -0.220 -O.'34O -0.535 -0.7-0

E p-COOCH3 Nitrobenzene -0.125 -0.250 -0.400 -0.610

AE 0.105 0.090 0.135 0.1302I

The electron-withdrawing substituent, -COOCH 3 , has a stronger effecton reduction of the nitro group in base than in acid. Substituentsthat change chemically with pH (e.g. COOH, OH) show even greaterdifferences.

The mechanism of reduction of the nitro group even in the first stepis not simple and is dependert upon pH:

1. -4--O + 2F + H20---P -NO + 20H-

2. -N=O + 2H+ + -2 •-NO + 2H20

Therefore, the changes in Fl at low pH reflect the effectiveness ofthe substituent on reaction22 and, at high pH, on reaction 1.

This change in half-wave potential (0.09 to 0.135 ) caused by intro-duction of the p-COOCH3 group in nitrobenzene gives an indicationof the magnitude of change that can be expected since this group isa relatively strong electron-attracting substituent.

There also have been quantitative correlation of polarographic datawith Hammett's sigma ( r-) constants (Refs. 3 ,4). The Hammettequation was modified to give the relationship of half-wave potentialto o0:

log k/ko CY- ( =AEI/ 2

L E is the shift in half-wave potential caused by a substituent, oris t~e polar substituent constant, dependent upon the kind and posi-tion of substituent, and P is a constant characteristic of thevteaction series.

This relationship is valid only for reaction series where the shiftin half-wave potential is due to polar effects. (inductive andresonance) of substituents. Where resonance and steric effects aresignificant, there will be deviation from the linear relationshipof A E. with 6 (e.g. OH on nitrobenzenes) since AEi is equal tothe suiR of the polar, resonance, and steric energies2

Thed"' constants have been correlated with several series ofreduction reactions (Refs. 3,4). The magnitude of•= is a measureof the susceptibility of the given reaction series to substituents.For example, substituted diphenyliodonium derivatives ( ,o = 0.02)(Ref. 1,4) reduce at pratically the same potential irrespective ofthe substituent. Nitrobenzenes (Ref. 3,4) are slightly affected bysubstituent groups. At pH <3,e'O = 0.16; at pH 5-8, 9 = 0.14; and atpH >11, t = 0.24.

14

These values of P reflect the influence of substituents on the rela-tive change in activation free energy between the reactant state andthe transition state since in irreversable reductions

•El . F*.

[Effects that change the free energy of the original state and thetransition state simultaneously and by the same amount are notdetected.] Thus, polarographic data indicate that the magnitude ofelectronic effects of even relatively strong electron withdrawingsubstituents on reduction potential of aromatic nitro compounds isnot large.

Zuman (Ref. 4) also reported a linear relationship ofa- with L E.

for some aliphatic nitro compounds (only four substituents cor- 2

related). (' values were 0.20 at pH 10.9 and -0.9 in 0.05 M H2S04.The negative value of (0 in acid indicates that the mechanism ofreduction of the aliphatic nitro compounds is different from that ofaromatic nitro compounds, which have a positive value of F in acid.

The negative t' value indicates that electron donating substituentsfavor the reduction. Thus, the activation step is predominatelydirect dissociation of a N-0 bond (SN1 ) whereas in the reduction ofaromatic nitro compounds (where (O is positive) the SN 2 mechanismpredominates.

In summary, the data on the relationships of r constants of substi-tuents to AEj can be used to indicate the magnitude of the polar

effect of substituents on the reduction (r), points out what sub-stituents affect the reduction by steric or resonance interactions(deviation of !Ej from A E, vs.o-plot), and indicate the type of

2 2mechanism involved in reduction (positive or negative f').

Attempts to correlate half-cell measurements such as open circuitpotentials, average operating potential, and coulombic efficiencywithcconstants were not successful. Apparently, other factors,such as variations in solubility of depolarizers in electrolyte ortheir absorbence on carbon overshadowed the effects due to polarityof the substituents.

The data collected to date from half cell tests, which reflect thetotal effect of the substituent, have been coded to enable compoundswith certain characteristics to be separated.

Data from half-cell measurements of compounds tested during the firstfour quartervi are summarized in Table 1 and of those tested duringthis quarter in Tables 2 and 3. Following are descriptions of themethods used tc measure the properties tabulated.

Energy Capacity in watt-min/g was determined by direct measurementwith a planimeter of the area under the discharge curves on the chrono-poteintiometric plots to a cut-off voltage of -0.6 v. In cell "D"tests, capacity was measured for both "A" and "B" levels. The valuethus measured at level "A" strictly speaking does not have thedimensions, watt-min/g since current density is higher at this level.The value given, however, gives a good indication of the suscepti-bility of the depolarizer to polarization.

Coulombic Capacity in amp-min/g was taicen directly from the chrono-potentiometric plots at a cut-off voltage of -0.6 v. Capacities forboth levels "A" and "B" in cell "D" are tabulated.

Coulombic Efficiency in % refers to the percentage of the theoreticalcoulombic capacity realized in the half-cell test up to the cut-offvoltage of -0.6 v.

O.C.V. vs NHE (Volts) is the open circuit potential of the depolarizerin the cell after predischarge of absorbed oxygen on the carbon. A20- min. wait on open circuit followed the predischarge period. Valuesin the tables that are starred (*) are open circuit potentials ofundischarged samples.

log was obtained between open circuit and the operating potential

for the given test. For tests in cell "D" operating current isusually 0.025 amp and in cell "C" 0.100 amp. Starred values (*) referto tests where there was no predischarge of absorbed oxygen.

Ave. Operating Potential (volts) was obtained by dividing the energycapacity by the coulombic capacity and subtracting 0.6 v from this Ivalue.

Drop in Potential in Each Quarter Time Period, %, is the percentageof the total drop in potential from the potential realized at start-up (at attaining operating potential) to -0.6 v.

Compounds are grouped below according to certain standards. Forcomparison, m-DNB has the following characteristics:

OpenCircuit

Ave. Operating Energy Cap. Coulombic PotentialPotential (volts) (Watt-min/g) Efficiency (volts)

in cell "C" -0.29 18.7 52.2 -0.08

in cell "D" (level B) -0.10 over 10 over 17 I

I6!

1. Compounds with average operatina potential over zero volts andenergy capacity over 11 watt-min/ (cell "C" or "D"). Most of theactive halogen ke.g. trichloroisocyanuric acid, t-butyl hypochlorite)and halogen addition compounds fall into this group. The only othercompournds are two acids: 3,6-dinitrophthalic acid (and its anhydridewhich hydrolyses to the acid in electrolyte) and 1-carboxymethyl-3,3,5,5-tetranitropiperidine.

2. 'Comounds which have an energy capacity over 20 watt-min/g incell "C". The group included the active halogen compounds plus thefollowing nitro compounds:

2,5-dinitropyrrole1,4,5-trinitronaphthalenepicric acido- and R-DNB

3. Nitro compounds which have average operating potential, energycapacity and coulombic efficiency greater than m-DNB when testedunder the same conditions.

2,5-dinitrobenzoic acid3,6-dinitrophthalic acid and its anhydride1,4-dinitropyromellitic acid and its silver salto- and R-DNBT-nitropyridinepicric acid1,4,5-trinitronaphthalene

4. Nitro compounds which were above m-DNB in average operatingpotential and energy capacity (but not coulombic efficiency) whentested under the same conditions.

1,4,5,8-tetranitronaphthalene2,5-dinitropyrrole

5. Compounds with open circuit potentials over +0.5 v. Most of theperoxides, active halogen compounds and halogen addition compoundsare in this group.

In addition, iodosobenzene, iodoxybenzene, 1,4-dinitropyrromelliticacid, its anhydride and its silver salt, 3,6-dinitrophthalic acid andi's anhydride, picric acid, hexylnitrolic acid, benzoquinone and 2,5-dinitropyrrole fall into this catagory.

B. EXPERIMENTAL PROCEDURE

The standard procedures for operation of cell "C" are given in theThird Quarterly Report and of cell "D" in the Fourth Quarterly Report.Oxygen was predischarged from the carbon except in tests where the opencircuit value was over 0.60 v (vs. N.H.E.). The period of dischargewas 5 min. at 0.1 amp in cell "C" or 20 min. at 0.025 amp in cell "D"

and was followed by a 20 min. recovery period on open circuit beforethe start of the test. The standard cathode sample consists of 0.5 gof depolarizer and 0.25 g of Shawinigan Acetylene Black (50% compressed).

Methods used to prepare depolarizers are given in the Appendix.

C. HALF-CELL TESTS

1. Halogen Addition Compounds Methods used to prepare these compoundsand a summary of their physical properties are given in the appendix.Data on shelf stability, both dry and in electrolyte, are given in !Section D. The new compounds prepared were selected on the basis ofexpected improvements in stability and increased capacity. The capa-city can be increased by addition of more than one molecule of halogento the parent and by minimizing the molecular weight of the parent sothat capacity approaches that of the free halogen.

Not all heterocyclics form stable addition compounds. For example, Iimidazole, r--, which contains two possible acceptor atoms for

Ihalogen, does not form addition compounds. Two heterocyclic compounds,1,10-phenanthroline and quinoxaline, were found to form relativelystable polyaddition compounds. The discharge characteristics of both Uthe simple addition compounds and of their salts were very similar toother perbromides tested (Figures 1-8). Both quinoxalinium chlorideperbromide and 1,10-phenanthrolinium chloride perbromide have slightly Ihigher energy and coulombic capacities than quinoline hydrochlorideperbromide. The quinoxaline nucleus also reduced partially at about0.1 volt in both compounds, (Figures 2 and 4). 1,10-Phenanthrolinealso appears to be reduced partially at lower potentials, (Figures 6and 8). The values for coulombic efficiency and energy capacity inTable 2 for both compounds are for reduction of the halide only. Itis possible that compounds of this type with higher capacities couldbe prepared by more efficient packing of halogen onto the parent nucleus.

The perchlorides have higher theoretical capacities than the perbromides, Ibut perchlorides prepared earlier had limited stability. Quinoliniumiodide perchloride, however, has been found to be stable. Its opencircuit potential, (Figure 9), is slightly higher than those of the Iperbromides and also higher than those of any of the less stable per-chlorides tested previously. This perchloride also reduces with highefficiency and has one of the highest capacities of the perhalogencompounds, (Figure 10). The compound polarizes during discharge more Ithan the perbromides, however, with the result that its average operatingpotential is only 0.61 v vs. NHE.

Several addition compounds (Figures 11-23) of heterohalides were preparedsince stability is expected to be higher for these compounds than forhomogeneous perhalides. The open circuit values of the heterohalidecompounds, IBr and ICl,on different parents varied more than the per-bromides (Table 2). The addition compounds with IC1 3 had higher opencircuit potentials, higher average operating potentials, and higher

8

capacities (Figures 11,13,15,18,19,20, and 23) than those of IC1 andIBr, (Figures 11,12,14,15,16,17,20,21 and 22). Capacities of the IC13compounds are also superior to the perbromides (Figure 13,19, and 23).All the heterohalides polarized more than the perbromides, with theresult that average operating potentials-are lower.

A series of half-cell tests in cell "D" at successively higher currentdrains were run with quinolinium chloride perbromide (Figures 25-27).Comparison of the data in the figures and in Table 2 shows that atlevel "B" very little polarization occurred on increasing the currentdrain eight-fold. Energy capacity dropped about 13%, but coulombiccapacity was maintained. The average operating potential was loweredfrom 0.93 v to 0.7 v, but the discharge curve was still flat; 94.8%of the drop in current in the test at 0.4 amp/g occurred in the lastquarter time period. Capacity and potential level at the bottomdropped sharply at current drains over 0.3 amp/g (0.75 amp/in2). Thisis in contrast to the result with quinolinium bromide perbromide(Figure 28 and Table 3) where level "A" maintained its potential forthe entire run at 0.392 amp/g. Level "A" in a test in MgBr 2 was low(Figure 29). In this test, however, level "B" was not functioningproperly owing to accumulation of gas bubbles. The descrepancy isprobably caused by local accumulation of gas, which interferes withelectrode readings. These readings then may not reflect the truecondition of the cathode at that point. In the test with quinolineperbromide (Table 3 and Figure 30) gas accumulation also interferedwith electrode reading at level "A". However, the data illustratethe ability of the perbromides to reduce with high efficiency at highcurrent drains. This is illustrated particularly in Figures 31 and 32where capacity is plotted against current drain for the quinoliniumchloride perbromide series.

Silver oxide and the silver salt of dinitropyromellitic acid werealso tested at high current drains (Figures 30 and 33 and Table 3).The perhalogen compounds have much higher operating potentials. Thesilver salt of dinitropyromellitic acid has the advantage of dis-charging with relatively high efficiency, but its operating potentialis low. The perhalides are superior to silver oxide in both operatingpotential and capacity in ammonium bromide electrolyte. (Silver oxideoperates better in 30% KOH than in ammonium bromide. Tests in KOHelectrolyte will be reported in the next period.)

2. Aromatic Nitro Compounds

a. Substituent Effects on Nitrobenzenes. Several substitutednitrobenzenes were tested in cell "D" since earlier tests with thisclass had been run in a variety of test cells and electrolytes, thusmaking comparison of cell characteristics with changes in electrondensity at the nitro substituent impossible. Some of the cellcharacteristics of the compounds tested are given below. Data arealso given in Table 2 and Figures 34-45.

9

AverageOperating Coulombic

O.C.V. Potential Efficiency Energy Capa-vs at of city at

N.H.E. Level B Level B Level BCompound volts. volts % watt-min/g

Sodium R-nitrophenolate 0.03 -o.46 24.3 2.08

p-Nitrophenol 0.07 -0.33 27.4 _ 5.2

Nitrobenzene -0.07 -0.34 29.3 5.92

p-Nitrobenzonitrile -0.01 -0.33 30.7 5.38

Sodium o-nitrobenzoate 0.01 -0.30 28.0 4.22r

Disodium nitroterphthalate 0.04 -0.25 38.5 4.32

The extremes in open circuit potential are separated by only 0.14 v.Sodium p-nitrophenolate has a higher open circuit potential thannitrobenzene, although the -ONa substituent is an electron donor andwould be expected to lower reduction potential. The values of opencircuit obtained in the cell, therefore, do not accurately reflectchanges in electron density at the nitro groups. There are probablyseveral reasons for this. Test conditions require predischarge ofadsorbed oxygen on the carbon and in most cases small amounts ofdepolarizers are also reduced during this predischarge period. Thus,open circuit values reflect the presence of reduction products. Alsovariability of solubility of depolarizers and their absorbencecharacteristics on the carbon electrode would affect their opencircuit values.

Average operating potentials have a spread of 0.21v. Sodium m-nitro-phenolate discharged at a lower potential than nitrobenzene and thesodium carboxylates at higher potentials. This would be expectedfrom consideration of their electronic effects. However, P-nitro-benzonitrile discharged at about the same average potential as nitro-benzene, although the nitrile group is a relatively strong electronacceptor. This discrepency again suggests that other factors affectingthe reduction of nitro groups are masking the electronic effects ofthe substituent groups. As noted previously, (Section IV, A) theelectronic effects are small. JThe reduction efficiencies of these compounds ran e from 24 to 3C%except for disodium nitroterphthalate, (Figure 45), which has ahigher efficiency.

The energy capacity of nitrobenzene is higher than that of any of thesubstituted compounds. Thus, although the compounds containing electron-withdrawing substituents in some cases were reduced with slightlyhigher efficiency at higher potentials, the increase was not enoughto compensate for the reduction in capacity caused by their highermolecular weights.

10

-Nitrophenol was tested for comparison with the sodium phenolate.e hydroxy substituent is usually an electron donor, but in this

molecule tautomerization involving the nitro substituent in neutraland acid media, results in a compound with a quinoid structure,

O=j=NOH.

It was found in previous tests (Third Quarterly Report) in cell "D"that o-DNB was about equivalent to m-DNB although the electroniceffect of the nitro group in the ortho position would be expectedto exert a greater influence than in the meta ?osition. R-DNB,(Figures 46 and 47) was also tested in cel-W--D. Its cell character-istics in cell "D" are similar to those in cell "C", tested earlier:initially, potential is higher than m-DNB, but potential drops moresharply with the result that the average operating potential andenergy capacity at level "B" in cell "D" is lower for the para isomer.

The above data together with data on dinitrobenzenes with carboxylatesubstituents in section "C" of this report indicate that the overallelectronic effect of the substituents on reduction of the nitro groupis minor and is often masked by other influences. Thus, experimentaldata agree with the conclusions reached in Section IV, A.

b. Aromatic Nitro-Substituted Carboxylic Acids. Testing ofcompounds in this group was extended. During the last quarter, itwas found that compounds containing one (or more) carboxylic acidgroups ortho to each nitro substituent were superior to compoundscontaining carboxylic acid groups in the meta position. For comparisonof compounds with carboxylic acid groups ortho and Para, o- and p-nitrobenzoic acid were tested (Figures 488,--79, 50 and Table 2). Theortho isomer is slightly superior in discharge potential, but the paraisomer is the superior depolarizer when judged by discharge level overthe entire test.

3,4-Dinitrobenzoic acid,

£OH

HN0,(Figures 51 and 52)

N0 2

3,4-Dinitrobenzoic Acid

is about comparable to 2,6-Dinitroterephthalic acid,

COOH

OO0H

2, 6 -Dinitroterephthalic Acid

I1

J

tested during the last quarter. Apparently the lower molecularweight of 3,N-dinitrobenzoic acid balances the slight beneficialeffect of the additional meta carboxylic acid group in the secondcompound. Both compounds are inferior to 3,6-dinitrophthalic acid,

N02

COOHr OOH00H

3,6-Dinitrophthalic Acid

which has a carboxylic acid group ortho to each nitro substituent.

The relative ineffectiveness of carboxylic acid groups in the metaposition is also shown in the data for 5-nitroisophthalic acid,

NO2NCC , (Figures 53 and 54).HOOC-OC 00H

5-nitroisophthalic Acid

The compound is inferior to p-nitrobenzoic acid and about equivalentto o-nitrobenzoic acid, both of which have one less carboxylic acidsub~tituent.

The data indicate that the most favorable configurations are thosewhere the nitro and carboxylic acid substituents are ortho or parato each other and where there is at least one carboxylic acid groupper nitro substituent. Para substituents may be slightly superiorto ortho substituents. Examples of compounds that should be or areknown to be superior depolarizers include:

O2COOH HOOC N02 HOOC..: N02 0 COOH

COOH HOOCU NO02 t,9OOH NO2

NO2 02 001*N0. OOH

Use would probably be determined by availability of the compound.

12

!

r c. Nitro-and Dinitrobenzenes substituted with Carboxylates orSulfonates

Several salts in this group have been tested. Data for carboxylatesof nitrobenzene were given in paragraph a. above. Data for disodium3,6-dinitrophthalate (Figures 55 and 56) and potassium 2,4-dinitro-benzenesulfonate, (Figures 57 and 58) are listed in Table 2. Thereis little difference in cell characteristics of the salts compared tothe corresponding dinitrobenzenes. All of the salts discharge athigher potentials initially, but potential generally drops moresharply during the test. Theoretical capacity of the salts is necess-arily lower than that of the parent compound, and it is found that thegains in efficiency from use of the salts are not enough to give anysignificant improvement in experimental capacity over the parent com-pound since the efficiency gain just about balances the loss due tohigher molecular weights. There is an advantage in use of the saltsin cells with magnesium anodes since as noted later in Section E, thesalts inhibit the corrosion of magnesium.

3. Trinitro-1-naphthoic Acids The three products isolated from thenitration of p-naphthoic acid (see Appendix) were tested separately incell "D" (Figures 59-64). The discharge characteristics of the threeproducts were very similar. The open circuit potentials were identical,(0.27 to 0.29 v). On discharge, Products 1 and 2 gave practicallyidentical chronopotentiometric relationships (Figures 60 and 62).Product 3 differed only in that potential dropped more steeply in thefirst quarter time period but leveled out to a flatter dischargeduring the remaining time than did products 1 and 2. All productsare better depolarizers than 1,4,5-trinitronaphthalene, which wastested in cell "C" during the Fourth Quarter. Both average operatingpotentials and open circuit potentials are higher. The data indicatethat the increase in potential due to the carboxylic acid g'oup isprobably mostly a pH effect since the different isomers had very similardischarge characteristics. The products are only very slightlysuperior to m-DNB.

4. 1.3.6.8-Tetranitrocarbazole

02 H

NNO 2

0202

Samples, which were obtained commercially, were tested in cell "C"(Figures 65 and 66). The compound has a theoretical capacity aboutequivalent to that of m-DNB and reduced with 40% coulombic efficiency,but the average discharge potential was only -0.44 v.

5. 4-Nitroimidazole

02 N

H

13

A sample of 4-nitroimidazole had been tested earlier in cell "C"(Fourth Quarterly Report). Partially reduced intermediates hadleaohed out of the cathode and reacted with the bromine at the anode,causing an early shut down of the test. This test in cell "D",(Figures 67 and 68) shows that 4-nitroimidazole is inferior to m-DNBand also operates at a lower potential than nitrobenzene. This isin contrast to 4-nitropyridine, which is a superior depolarizer. Theimidazole nucleus is more acidic than the pyridine nucleus and the4-position is relatively electronegative with respect to the nitrogenatom.

6. Sodium Salt of Nitranilic Acid

Na O* y2

This compound, which was obtained commercially, was tested in cell"D" (Figures 69 and 70). It can not be said definitely whether bothtypes of active groups or only the nitro groups are being reduced.The coulombic capacity is slightly higher than theoretical forreduction of the quinone linkage alone (11.7 amp-min/g). Since thedischarge curve is flat with no break in potential, it is possiblethat the entire discharge is from reduction of the nitro substituents.The discharge characteristics, however, are inferior to those of m-DNB.

7. N.N'-(l.2-Ethylene)bis maleamic Acid

(HOOC-CH=CH-J-NHCH 2 -]2

This depolarizer, obtained from the Sample Recording Center ofMonsanto Chemical Company, was tested in cell "C" (Figures 71 and 72).Each unsaturated carbon-carbon linkage in this compound is activatedby the adjacent electron-withdrawing carboxylic acid and amide groups.Both reduction potential and efficiency were low and are inferior tothose of tetracyanoethylene, which was tested previously. The fournitrile groups in the later compound are therefore more effective inactivating the unsaturated linkage than one carboxylic acid plus oneamide group.

8. Phosphomolybdic Acid

20 MO0 3s2H 3 P0 4 "48H2 0

The commercial sample has the above empirical formula. The sampleweight used for the test was adjusted to compensate for the water ofhydration: 0.62 g of the salt corresponding to 0.5 g of anhydrous20"MoO3 '2H3 PO 4 was used in the test in cell "D" (Figures 73 and 74).The compound has a high open circuit potential, 0.69 v, and polarizedvery little on increasing the current to operating potential (Figure 73).However, the potential dropped sharply after a short time at 0.05 amps/gwith the result that both coulombic capacity and energy capacity werelower than those of m-DNB.

14

.!

II

9. Peroxides

Several peroxides were tested in cell "C" during the Fifth Quarter.Open circuit potentials of peracetic acid, CHsCOOOH, p-nitrobenzoyl

I peroxide,

[0ON4G CO0] 2 0 and benzoyl peroxide, [ -O4 0C]2O, were

high, but all polarized appreciably at even moderate current drains.These peroxides have been retested this quarter in cell "D" (Figures

I 75 through 78).

Polarization of both p-nitrobenzoyl- and benzoyl peroxides was thesame at 0.025 amp, (0.127 amp/in2 ) (Figure 75). However, theunsubstituted compound was more polarized at lower currents. There-fore, it is possible that another substituted benzoyl peroxide mightreduce at higher current drains with less polarization. Peroxideshave the advantage of high initial potentials and the disadvantage oflow coulombic capacities since reduction involves only a 2- electronchange.

I 10. m-Dinitrobenzene in Electrolyte with Added Methanol

An attempt was made to improve the 6ell characteristics of m-DNB byincreasing its solubility in electrolyte. A previous attempt hadbeen made in cell "C" (Second Quarterly Report). Reduction efficiencywas found to be lower in the presence of methanol. This lowering ofefficiency was attributed to loss of m-DNB from the electrode site byleaching out into the large volume of electrolyte used in cell "C".

Tests in cell "D" with standard ammonium bromide electrolyte containing10% and 20% methanol (Figures 79 through 82) show that the addedmethanol caused lower cell efficiencies, with the greater decrease inefficiency in the 20% methanol test. Apparently the methanol exerteda greater detrimental effect on some phase in the reduction mechanismthan the beneficial effect on the mechanism by increased solubility

I of the m-DNB. It is probable that the absorbance of m-DNB on thecarbon was lowered by preferential absorption of methanol by the carbon.

11. Ferrocene

Ferrocene was not reduced in a test in cell "D" (Figure 83). It wasdifficult to wet, and the sample had to be shaken with electrolyteand carbon containing a few drops of methanol before loading into thecell. The ferrocene is probably not absorbed by the carbon efficiency.

1 15I

Sb

12. Depolarizer Mixtures

Two depolarizers with different discharge characteristics when mixedtogether were found earlier (Fifth Quarterly Report) to dischargeindependently of each other. Two systems where there is a combinationof electrochemical reduction and chemical reaction of components in amixture have been tested. The first system was chosen because itoffered the possibility of increasing the discharge potential ofiodine (and possibly bromine). Compounds of the type RSI are knownto be reactive oxidizing agents, but have limited stability.Discharge potential is expected to be high based on discharge potentialsof other compounds tested containing halogen in the +1 valence state.These compounds can be prepared in situ by several routes:

RSNa(or H) + 12 b. RSI + NaI-CSI

'C=S + 12 ""C \I

MS(e.g. CdS) + 12 -* MSI

Only a small amount of the sulfur compound is required since it isregenerated on electrochemical reduction of RSI. Two tests were madewith iodine, one with 0.1 g of CdS added and the other with carbondisulfide added. The data for iodine (Figures 84 and 85) and theCdS-1 2 mixture (Figures 86 and 87) show that the added sulfide didnot increase the discharge potential, but caused a lowering in effici-ency of reduction. Carbon disulfide, also, gave no increase in dis-charge potential. It is possible that the concentration of RSI istoo low compared to the concentration of iodine to be detected. Asystem operating at very low current drains might be able to takeadvantage of this mixture. Also, a special cell where iodine con-centration at the electrode is minimized (e.g. by continuous addition)should be operable.

The second system was designed to increase the capacity of a depolarizerby use of a mixture of depolarizer (quinone) with a chemical (2-DNB)that regenerates the depolarizer by chemical oxidation of its reducedform. The system operates since the depolarizer (quinone) reduces ata higher potential than the oxidant (o-DNB) under these cell conditions.

oHH

+ 2 + 20H- -- NO + 2 + 3H2 0

OH 0

16

For each mole of o-DNB, 3 moles of quinone can be reduced with a totalchange of 6 electrons. The capacity of a 2:1 mixture of benzo-quinone o-DNB is thus 83.9 amp-min./g compared to 30.7 amp-min,& forbenzoquinone alone. (This does not include the additional capacityfrom complete reduction of o-DNB, but assumes complete utilizationof o-DNB in the regeneration reaction.)

Tests in cell "D" with benzoquinone (Figures 88 and 89) and with amixture of benzoquinone and o-DNB (Figures 90 and 91) indicated thatthe regeneration system was operating slightly since the mixture,containing 0.28 g of benzoquinone remained above zero volts (atelectrode level C) for 135 minutes, which is the same time as in thetest of benzoquinone (0.5 g) alone. The mixture then discharged atthe level of o-DNB without completing the regeneration reaction. Atest with chloranil was less successful. A test of chloranil,alone, in cell "D" is illustrated in Figures 92 and 93.

The chemical regeneration may be slow at room temperature. Therefore,tests in cell "C" at 500C were run. (Figures 94 and 95). However,under these conditions benzoquinone polarized very quickly (Figure 95).The discharge curve of the mixture is close to that of o-DNB. Thereis a possibility that this system could be developed by improving thecell conditions to promote the chemical regeneration reaction. Slightchanges in pH of the electrolyte thigh pH may favor regeneration) maybe advantageous. Also, improvement in contact of reagents is probablynecessary. A higher ratio of o-DNB in the mix may be necessary.More efficient methods of mixing the reagents should be tried. Forexample, an ether or alcohol solution of benzoquinone could be mixedwith the carbon, the solvent evaporated, and o-DNB added to thecarbon and mixed.

Polynitrobenzenes form molecular complexes with most aromatic compounds.Use of a compound such as the one shown below would insure reagentcontact.

0aNN02O2WN •-N02

13. Leuconic Acid

O=C C=0 "I.2H2 00=6 C0O

The preparation of this compound is described in the Appendix. Asample was tested in cell "D" (Figures 96 and 97). Although completereduction of the five carbonyl groups to hydroxyl groups is possible,the half-cell data indicate that probably only the first one or twoare reactive under these cell conditions.

17

I

D. STABILITY OF HALOGEN ADDITION COMPOUNDS IN DRY STORAGE AND INELECTROLYTE

Stabilities of most of the halogen addition compounds have beenmeasured after periods of storage both dry and in 1:1 MgBr 2 .6H 2 0:H20.Stability was determined by analysis for active halogen content bythe standard iodometric method. Aqueous ethanol was used for thesolvent during reaction of potassium iodide with the sample. Thedata are summarized in Tables 4 and 5. These data and those obtainedpreviously lead to the following conclusions:

1. Addition compounds of halogens on strong bases are stable tosimple dissociation, but may be susceptible to intramolecularreactions with resulting loss of activity. This is illustratedby the decomposition of pyridine perbromide through intramole-cular reaction.

2. Electron-withdrawing substituents on the parent stabilize theaddition compound against intramolecular reactions, butdecrease stability from simple dissociation, especially inaqueous solution. Thus, 6-nitroquinoline perbromide is stablein dry storage, but dissociates slowly in aqueous solution.

3. Complexes of the type ;NHXX 2 , where X is any halogen are themost stable both in dry storage and in electrolyte. Additioncompounds such as trimethylammonium chloride perbromide,quinolinium chloride perbromide and quinolinium chloride per-chloride are very stable. Compounds with a weak base asholder, such as quinoxalinium chloride perbromide, are morestable than the simple addition compound, i.e. quinoxaline per-bromide, but do not have unlimited stability.

E. CORROSION TESTS

Further tests to ascertain the inhibitory effect of tetrasodiumdinitropyromellitate on magnesium have confirmed the earlier results,reported in the Fifth Quarterly Report, that the salt is a stronginhibitor of corrosion of magnesium. It has also been found that otherwater soluble nitro compounds such as potassium 2,4-dinitrobenzenesulfonate and disodium dinitrophthalate also inhibit corrosion ofmagnesium.

Extension of the first tests reported previously to two months showeda greater contrast in the Az-10 magnesium cans that had been immersedin:

(1) magnesium perchlorate electrolyte containing lithium and

barium chromate inhibitors,

(2) the electrolyte described in (1) saturated with m-DNB, and

(3) the electrolyte described in (1) containing 25% by weighttetrasodium dinitropyromellitate.

18

The results are illustrated in Figures 98. The can treatedas in (1) above was extensively corroded so that it had broken open.The can treated as in (2) above was almost as bad as can (1), althoughcorrosion was not quite as extensive. The can in (3) showed very littleindication of corrosion. Only minor pitting was visible.

Shorter time tests with potassium dinitrobenzenesulfonate and disodiumdinitrophthalate show that these compounds are also effective inhibitors.

Tests were also run in the absence of chromate inhibitor. Under theseconditions magnesium cans in 2M perchlorate are completely convertedto magnesium hydroxide so that no water was left within 12 days.Corrosion of cans in solutions saturated with m-DNB was the same. Acan immersed in the same electrolyte containing tetrasodium dinitro-pyromellitate (without any chromate inhibitors) showed only minorpitting after 12 days exposure. Thus, inhibition is effective in theabsence of chromates, although the presence of both chromates andsoluble nitro compounds affords the maximum protection. (Figure 99).

F. REFERENCES

1, 9,58Pgk§ 404 Hl, M, fiutrm~n; "Th Fp@ MnP of Bom@ Orgnic

91fA) g@ J. W, 6mith 4nd J. 0.W1~jJPyQm _W54

,, H, Jdffe, ChM, _ _V_,, -U 191 (19N)

V. PROONAM FO NEXT QUA&T-R

Th@ abi@rbence of several nitro compound@ by hawinigan Black will bem@&sured to dtmin@infIA depo ariger §tV96ure oola1tes withmagnitude of ab@orbena@. OCmpound@ with oonjugat@d struatuos•milarto the carbon skeleton, suoh A@ nlitr nfthrAcen@; nitopyren@ and nitro-triphenyl@ne will be compared to nitro compounds with aimpler structuressuch as m-DNI, totramodium dIn tropyromellItate, and nitropropane,

For the screening program, nitro-Bubutitutod aromatic carboxylic acidssuoh an the nitrobenzoio aoids, 3-6-dinitrophthalic acid, and 1,4-dinitropyromollitic acid will be esterified to determine whether thesecompounds are superior to the @odium ealts as depolariu@rs.

The following compounds listed are on hand for testingi

Benuenearsonio aoid GsADOH! -OH

19

NC OTricyanohydroxyethylene C=C

NC"- 11O1H

Tetraethylethylene tetracarboxylate 25C-,CC O2H

C2 H5 OOC-- ~'OOOC2H5

1 ,4 k,4-Tetrapheny1 1,3-butadiene ( -C=CH-CH=C-(J

Phenylisothiocyanate 'C3ýNCSJ

Dirnethyiglyoxime H3C-C-j9-CH3NO!" NO'H

Nitrated polystyrene 102 [OCH- + 2N&CH-0H2-]n

5-Nitrobarbituric acid 0

H

N,-N-Dicyclohexylcarbodiimide O -==N

Nitrourea H2N-8-NHNO2

Cyclooctatetraene cDiethylazodicarboxylate EtOOC-N=N-COOEt

OOH OH

Cyolohexanone peroxide 0I-0~:

20

t-Butylperbenzoate ( c!ý--O0t-Butyl

0t-Butylperacetate CHm-&' OOt-Butyl

Methylethyl ketone peroxide

7,7,8,8-Tetracyanoquinodimethan (NC) 2 C@ C(CN) 2

COOHIHNfc OUH

Uracil-4-carboxylic acid 0= "b0

\N/

H

VI. CONFERENCES

6 November, 1962

Mr. S. J. Bartosh of the U. S. Army Electronic R/D Laboratory visited

the Boston Laboratories of Monsanto Research Corporation to review theprevious quarter's work and also to plan the future program.

14 December, 1962

Mr. B. A. Gruber, Dr. J. 0. Smith and Mr. F. J. Winslow of the BostonLaboratories of Monsanto Research Corporation visited the U. S. ArmyElectronic R/D Laboratory to review current work.

VII. IDENTIFICATION OF PERSONNEL

Name Job Title Hours Worked

B. A. Gruber Project Leader 108

J. 0. Smith Manager, Physical Chemistry and 20Engineering

J. E. Harris Senior Research Chemist 56

E. A. McElhill Research Chemist 436

J. H. Him Laboratory Technician 431

Other Personnel 7

Total 1058

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Figure 4 Chronopotenticietric plot of quinoxalinium chlorideperbromide in cell "D' in 168 g/il NH4Br electrolyteat 0.05 amp/g. 39

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04 )C

-P0

94H

r4

41.4

4o1

:AL

0.8- Test 37201

ElectrodeLevel

0QAAve. B&C

o4-3

0.

.0

01.2 Br2

00

4.3

21M 36V Time, min.

5 10 15 Cap. ,arnP-min/gI Figure 6 Chronopotentiometric plot of 1,10-phenanthrolineperromde n cll"D' in 168 g/l NH4Br electrolyte

at 0.05 amp/g. 4

0

fI c

4) 40

V 0. 00040 H I-4.

t- P,

I~a04.)

-4-

.430

F4,

-t4

:4

424

~s

Test 37202

ElectrodeLevel

1.0 "

So.6 -z XHCI y Br2

>' 0.4

0 o'0.2

0

O,

0[0

-0.4

IlI I I , I1 i0 200 300 Time, min.

5 10 15 Cap.,amp-mir/gFigure 8 Chronopotentiometric plot of 1,10-Phenanthrolinium

chloride perbromide in cell "D" in 168 g/l NH4Brelectrolyte at 0.05 amp/g.

43S|

Ii

14,

H0

.020 0J

*H4. H.-.- 4)

4) \

81.443L

0I

'-H4,P

433 O

H H0

~ CdH.-

U-H

443

1.0- Test 37233

Electrode

Level

0.8

0.6

o.C'0

0.2

-40)04

W0

-0.2-NHIC12

-0.6 -

I ... I ,, I I . ,Ip

o100 00 3005 10 15

Figure 10 Chronopotentiometric plot of quinolinium iodine per-chloride in 168 g/1 NH4Br electrolyte at 0.05 amp/g.4•5

*0

0.C

10 10 F)

0 1004),- 14 10 .

r44 .0 ý-

0'9 0 0

-4 -4 -4.-

-4 -4 -4 (d-

'0 4) 4) 4 4)00 0 '0 '0

.0 0 10 4H

a 0 0 0 4

0.)0 0 V 0

-4 -4H 4044-H H4 H0 0 0 Ln

4)0$4 t) 0

r,80 ~0002 C

'0

0 r4) 04,4

0,~4 .OH

4.),l4

F4.00 cm :3

0*-H

H,

F4

00

HH0 0 0 0 0(SIToA) allt 3A tTUT~uoO4d P04;MO

46I

i-

Test 384120.8

ElectrodeLevel

0 AAve. B&C

0.6

o4-

-0.2-0

0.

H~ O

-0.843ý

-o43

-0.6-

-0.8-

0 100 200 300 Time, min."5 10 15 Cap.,amp-min/gPigure 12 Chronopotentiometric plot of quinolinium chlorido

iodine bromide in cell "D" in 168 9/1 NH4Brelectrolyte at 0.05 aaup/g

4

Test 38410

1.0 ElectrodeLevel

A

0.8-

0.6J

z

. 0.2- HCL, IC13

r O.C-S~I

-0 .2 - I

-0.( r

aI.,II I I --- I I , I0 100 200 300 Time, min.5 10 15 Cap. ,amp-min/gFigure 13 Chronopotentiometric plot of quinolinium chloride]

iodine trichloride in cell "D" in 168 g/i NH4Brelectrolyte at 0.05 amp/a484

iI

0.8 Test 38itO9

ElectrodeLevel

0.6- BSC

0.4JH

0.2

a 0.2-W HCI ICI

,•0.A -

-o.6-

-0.6

-0.8

i I I , I I0 100 200 300 Time, mir.

5 10 15 Cap.- rimp.min/gFigure 14 Chronopotentiometric plot of quinolinium chloride

iodine chloride in cell "D" in 168 g/l NH4Brelectrolyte at 0.05 amp/g

49

04 H

OHJ

co H10HH r-r

ivi'0 t.,

on -4 ;.4 0 ý4) 0 0 a 1

'0H H .

U 0 0 .404 r4 .4 Hc

4. 4J 0 -

i00

no 0 0 H0 0

0 0 0 0.4~P 04.4

0 000V4.3> 4 Pn 0 4.4,4 I 0

104.4-)l 04) 00 D 00 .00ý

~~U)

0-4r. 00 H H 00 4-

(9!1'[Q,&i'0di0 IiiC Q4~~ P110

H500

II

0.8 Test 38405

ElectrodeLevel

o.4-

H

0.0.2-

o.4

•-o.6-

-0.6

-0.

7"0 I 200 300 Time, min.5 10 15 Cap.,amp-min/g

Figure 16 Chronopotentiometric plot of quinoline iodine bromidein cell "D" in 168 g/l NH4Br electrolyte at 0.05 amp/g

!51

0.'6 Test 3840ol

Electrode

Level

o.4- B

o ICI

0.2

H

0

4-1.

-0.8

I I I I I S

0 100 200 300 Time, mi.5 10 15 Cap.,Pip-mln/g

Figure 17 Chronopotenticmetric plot of quinoline iodine chloridein cell "D" in 168 g/l NH4Br electrolyte at 0.05 amp/gr

52

1.0

Test 38402

ElectrodeLevel

0.8

C

0.0

-4

01

0.4

0.2

o Id 3s

" -0. I

-0.(

0 100 200 300 Time, min.5 10 15 Cap.,amp-min/kg

Figure 18 Chronopotenttometric plot of quinoline iodinetriohloride (Sample A) in cell "D" in 168 g/lelectrolyte at 0.05 amp/g

5V.

1.0 Test 3480ol

Electrode

0.8- A

BI0.6

0.1)-43

S0.

o.4-[

0.21

'43

o IC1

V° ,4-2 -0 .2

-0. 1

I

0 100 200 300 Time, min.5 10 15 Cap.,amp-min/g

Figure 19 Chronopotentiometric plot of quinoline iodine tri-chloride (Sample B) in cell D" in 168 g/l NH4Brelectrolyte at 0.05 51fp/g

I

IUI

* u-P

*14

004

Ma 0

o a 0

-1 4 %41

.4 0 00W

ac

43 ot 4 t.T; S.iii illI-~~~~r c3 *4400q

4394

* 3

wiN

M 0 0 0 0'

8ti A TV4UIU.l OI POMIWO4

55

IM

Test 384080.

ElectrodeLevel

B

0.

! 0

,.¢ 0(CH3 ) N.HCL"IBr

4 3

4-0

0

04,

0*'C

Cd

0 100 200 3005 10 15

Figure 21 Chronopotentiometric plot of trimethylammonium chloride Iodinebromide in cell "D" in 168 g/1 NH4Br electrolyte at0.05 -mph.

56

I

0.8 Test 38406

ElectrodeLevel

'- • A

o.6- B0 C

0.2-

-H0-4

4)

0

0-02

-.4- (H )N,~-~

6 -

5 10 15 Cap.,amp-mini/gFigure 22 Chronopotentiometric plot of trimeth~y1 ammonium

chloride iodine chloride In cell "W'in 168 g/lNH4Br electrolyte at 0.05 amp/g.

57

•ob

Test 38407

ElectrodeLevel

o.8- C

0.6-

0.4-

(CH3 ) 3N.HCI.IC1 3

-0.•

4)

-0.• I0

0 I

100 200 300 Time, rmin.5 10 15 Cap.,amp-mil/g

Figure 23 Chronopotentiometric plot of trimethylammoniumchloride iodine trichloride in cell 'D" in 168 g/1NH4Br electrolyte at 0.05 amp/g.

58

7 0

0

0000

t'-4

al 0 000

Cu 0 r.C

0)

~06000

00

214)044H

00 ~S00

04)

0- H

bH

H

14

4)H

qbJC; C; C; C

(94TA) -j -H'K iA TTWO1d QPM40

Electrode CurrentTest Level amp/g.

37222 A 0.0500.050

C 0.050

37235 9 A j.0B 0.100

0.-37236 A 0.150B 0.150

r 0.150

o.4-

0

,-1. 0

r 0-

o-0.2-

4 -

C~-o.6-

FC1 Br2

II -- I - - I 1

1020 30 TVme,rl nFirure 25 Chronopotentiometric ploto of quinolinium chloride

in cell ""O in 1563 /l/ 1H4 iBr electrolyte at 0. 050,

0.100 and 0.150 mxp./g.I6o I

II

Electrode CurrentTest Level amp/s,

0. 37237 A 0 .25C 0.250137238 A 0.0

. C0

,-4

IwIz

I0

0 .0

0

-0.

I .HClBrg

-OB -

I .0 20 4o 60 time, min.

Figure 26 Chronopotentiometric plots of quinolinium chlorideperbromide in cell "D" in 168 g/l NH4Br at 0.250 and0.300 amp/9. 61

I

Electrode Current

Test Level amp -A

08. 37239 A 0.350

00350

37239 * A 0 .4o0B 0 k400

o0003

0

4.3

0

-0.2

43.4

-0.8

0 10 20 30 me,mn.

Figure 27 Chronopotcntiometric plots of quinolinium chloride per-

bromide in cell "D" in 168 gIl. N114Br electrolyte at

0.350 and 0.400 amp/g.

62

E-4 0

t-. 0 ,

P(\ F (

S4

n1 0194

' 0 C

-44I'\ 0v

,0

0

4 4 F4*

ON 04.

r.4 C'O0

00

14-

* 0

0~~- C; 00

(O~tOA) -H'M -A '[-t2S40dOP01149

63)

E-4U E

0 0.;(M 0 `4t~Cuj V r.H

-P Q

to 4)00

-4

0

t(r- Ol

0

0

'43

-H9.0.

-P4C

00

H~ 0

CL0

.00

6~ 6 0(u~~~coA)7 .M BAtTUiO pqu

I

ElectrodeTest Level Compound

34945 B Quinoline0.8 - C Perbromide

37219 A SilverB Oxidec

0.6

0B22

0.4-

ý0.2

r

@o

HOg

0

-o.42I

0L

-0.6

-0.8

I I, I I

0 10 20 30 Time, min.3.92 '(.84 1i3.6 Cap.ap.mizv'g

Figure 30 Chronopotontiometric plots of quinoline porbromido andsilver oxide in cell "D" in 168 g/l NH14Br clectrolytpat 0.392 amp/g. 65

Current"Test amp./g.

o.8 - 37222 0 0.05037225 0.10037237 0.25037240 O.400

o.6

0.4 -

4-H7

•0.2-

z1

'0

o HClBr 2

0

-0.4-

-0.6

-0.8

2, 10 Cap.amp.-min/g.

Figure 31 Effect of increase in current on coulombic capacityof quinolinium chloride perbromlde at level C incell "D" in 168 r'/l NH4 Br

66

!

CurrentTest amp./g.

0.8 37222 0 0.05037235 0.10037237 o0.25037240 o.4oo

0.6

o.4

0.2

0

-0.2

HCl Br 2

-0.4

-0.6

-0.8!I II ,

0 2. 10 Cap.amp.-min./g

Figure 32 Effect of increase in current on coulombic capacity ofquinolinium chloride perbromide at level A in cell "D"in 168 g/l NH4Br 67

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Figure 78 Chronopotentiometric plots of peracetic acid Incell "D" in 214 Mg(OlO4)2 electrolyte at 0.05 amp./9..113

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120

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132

I WITH CHROMATE INHIBITORS

' Sat. with 25% TetrasodlumBlank m-DNB Dinltropyro-

-- mellitate

!

IA 2A 3A

1 Week Exposure

IB 2B 3B

1 Month Exposurei"

i ?'1

!

I ic 2c 3c

2 Months Exposure'I;• Figure 98. Results of Corrosion Tests on AZ-IO

Magnesium Size A Dry Cell Cans.With Inhibltor.

j• • MONSANTO NES[ANCH CORPORATION •

WITHOUT GHROMATE INHMITORS,

Tetraxodium 25% sodl fu -Tllnitropyro- 3,6-Dinitro-

Blan melitat phtalat

3 L-1-A L-2-A12 Days Exposure

Sat. withm-DNB

53 Weeks Ex~posure

25%Tetrasodiura DisodiumDilntropyro- 3,6-Dinitro-mellitate phthalate

L-1-B L-2-B

1 Month Exposure

Figure 99. Results of Corrosion Tests on AZ-10Magnesium Size A Dry Cell Cans.Without Inhibitor.

0 WMONNTO RESEARCH CORPORATION 0

VIII. APPENDIX

A. METHODS USED FOR PREPARATION OF COMPOUNDS TESTED

1. Halogen Addition Compounds

The simple addition compounds of the type"NX2 , where X is anyhalogen atom, were prepared by adding a slight excess of the halogen(as gas or in chloroform or carbon tetrachloride solution) to achloroform or carbon tetrachloride solution of the free base, "'N,at room temperature, filtering the resulting product, washing withsolvent and drying at room temperature.

Compounds of the type 'NHXX 2 were prepared in the same way by additionof the halogen to pulverized salt, •NHX, in carbon tetrachloride orchloroform and allowing the mixture to stand overnight. The productwas recovered by filtering, and washed with solvent and dried at roomtemperature. The salts, 2NHX, were prepared from the correspondingfree bases by direct addition of HX to the free base in chloroform orcarbon tetrachloride solution.

The addition compounds were analyzed for active halogen by reactionwith KI. In some cases, the experimental value does not correspondto a 1:1 addition compound, in some cases being higher and in otherslower. This difference could be caused by either retention of more orless than one mole of halogen by the carrier or by partial exchangeof halogen in the HX of the carrier (e.g. may contain some

HI C12

S-). Analyses for total halogen in individual cases could

S~ HCICI2

resolve the cause. The experimental values have been used for cal-culation of coulombic capacity. Data on compounds prepared this quarterfollow (see next page). An attempt to prepare bromine addition com-pounds of 4-nitroimidazole was unsuccessful.

I

II135

i- Ji

r. . .

0 ý

HH

OD 0U 0H H 0 H _a

4-) '- C 0

O0 0 0

0 0 0 0 0 r.

0~~ H- --CV 0) 0)d )PV

H CV H

co d)o

4.)

0'-4

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00 0

r- 04-

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0 -4 0 0 0Hl Vo H- H

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0 0 0ri 0 0) T4 00

H H-0 - '-H V

r.r .V~I 4-H vi4 9l q0H H H 2C2 H4 H4 r

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& & & & &136

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0

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rH r-U H ~

4)t4'

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034 0 0

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0 ) 00L -'.04

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10

!2. Leuconic Acid

Leuconic acid was prepared by oxidation of inositol with nitric acid,using the procedure of Contardi (Ref. 1). A mixture of 20 g. inositolin 60 ml 90% HNO 3 was refluxed for 30 minutes and then the solutionevaporated to dryness on a steem plate. The product was dissolved inwater, precipitated with ethanol, filtered and washed with ethanol.Solvent was removed by evacuation for 1 hour at 10 mm. followed by90 minutes at 0.2 mm. at room temperature. The final product, ahydrate, had an elemental analysis corresponding to C5 05 • 1.2H2 0.

3. Salts of Acids

The salts of benzene carboxylic or sulfonic acids were prepared bytitrating aqueous solutions of the acids to a phenolphthalein endpoint with sodium (or potassium) hydroxide, and recovering the saltby evaporation to dryness on a steam plate.

4. Trinitro-B-Naphthoic Acids

Dhar (Ref. 2) reported preparation of two, unidentified isomers oftrinitro-p-naphthoic acid by nitration of p-naphthoic acid. UsingDhar's procedure, 125 ml. 70% HN0 3 was added to a slurry of 10 g.p-naphthoic acid in 200 ml. conc. H2 S0 4 slowly until the temperaturereached 85 0C and there was complete solution. The solution was cooledand kept at 30-400 until all the nitric acid was added and the solutionallowed to sit 4 days. The solid product (product 1) which separatedwas removed by filtration and the filtrate poured onto ice. Product 2was removed from the aqueous acid by filtration. Addition of morewater to the filtrate precipitated product 3. Data on the productswhich were not analyzed or identified further, are below.

Weight AcidProduct Color mp, OC* Grams Equivalent **

1 Yellow 259-61. 3.5 3002 Pale 200-215 3.6 305

Yellow (d)3 Yellow 190-215 3.1 310

(d

* Dhar gives product 1, mp 2200 and product 2, mp 2150.

• Calculated for trinitro substituted acid is 307.

IX. REFERENCES

1.) A. Contardi, Gazz. chim. ital. 51, I, 109 (1921); C.A. _5, 3073.

2.) S. N. Dhar, J. Chem. Soc. 117, 1001 (1920); C.A. LA, 34o4.

139i!i

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I4

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s.~4m 5~ . ;D~u 3C ~ ~ @*4-