THE I)OLAROGRAPHIC STUDY OF SOME SIMPLE

,Nlrl'U OP ARA FFINS *)

by F. PETRU.

Alt.hough the electro-reduction of arOll1atic nitrocOlnpounds, especially of nitrobenzene, has been subject of many investigations, carried
out both in the ordinary electrolytic way 1) 2) as wel l as polarographically,3) 4)5) but little attention bas been paid to the polarographic study
of a liphatic nitroconlpounds. Th. de Vries and R. W. 1wett6 ) studied
the electro-reduction of simpJe nitroparaffins at the dropping mercury cathode by plotting the current-voltage curves, which resulted
fronl hand adjustment, the electrolyte consisting of 0,05 m.H 2 S04 or
-LVa/3()4; the nitroparaffin concentration varied from 0,0005 to 0,017 m.
These authors found the diffusion currents to increase in acid solutions linearly with the concentration, in neutral solutions there were
deviations frOJTI the linear relationship, ascribed by the authors to
a partial change of the nitrobody into its aci-form. The haJf-wave
potentiab were determined and found to be close so that the individual
nitroparaffins in a mixture could not be distinguished. The electrolytic
reduction of some simple nitroparaffins was studied for preparative
purpm;es by P. Pierron,?) who ascertained that at room-temperature
only the corresponding N-alkyl-hydroxylamine is formed, whereas
at 75 C the reaction proceeds right to the am ino.
As in the recent time comparatively simple Inodet; of preparation
of pure nitroparaffins Jlf1ve been found 8 ) and their use considerably
jncreased, it hat; been thought appropriate to investigate in detail the
polarographic behaviour of ~mch cornpounds in order to obtain results
which might bo useful from t.he general as well aH analytical point
of view.

'rho compounds here used were nitromethane, nitro ethane , I-nitro propane and I -nitrobutane. The nitromethane was prepared in the
mmal way9) from monochlor'acetic acid and sodium nitrite. After re *) Pul)li shed jn Czech in Oherniclce Listy 41 (1947) 255 - 262.

621 --

peated distillation in a Widmer' s colurnn it had the b. p. 100- 100,5 0,

(741 mms); d 20 1,1388; n;'l 1,3811.

Nitroethane b. p. 112- 113 0, (745 mms); d20 1,0510, nlll,3909 was

prepared in an analogous manner10 ) from cx-bromopropionic acid and
sodium nitrite.
I -Nitropropane and I-nitrobutane were prepared according R. B.
Reynolds and A. AdkinsU ) by the action of silver nitrite on the
respective alkyl bromides.*) After repeated distillation in a Widmer 's
column the products had the following properties:
I-Nitropropane had the b. p. 128- 129 0 (747 mms); d 20 1,0042 ,
n'b 1,4003 and I -nitrobutan b. p. 43- 44 0 (11 mms); d 20 0,9737 ,
n~Y 1,7098.

The polarographic current-voltage curves were registered by Ineans

of a polarograph from Dr. V. and J. Nejedly, Prague. (1 mm de flection of the galvanometer corresponded to 2 X 10- 9 amp., when maximal sensitivity was used.) The thickwalled capillary had a bore of
0,09 rnm in diameter and was 10 ems long. The solutions were examined in a Kalousek vessel,I3) having a saturated calomel electrode as the anode.
Besides the ordinary current-voltage curves the oscillographic potential-time curves (n - t) and the corresponding derivative curves
(dn /dt - t) were also investigated. The latter type of curves was
studied by means of a Philips cathode-ray oscillograph, according to
J. Heyrovsky and J. Forejt using the streaming luercury electrode. H ) The curves were registered photographically by the Rolleicord-II camera, with an exposure of 1/ 25 sec. (on Agfa-Isochrom-Feinkornfilm 18/10 0 DIN).
Solutions of the paraffins consisted of a set of buffers prepared
according to the universal B I' itt 0 n -Rob ins 0 n mixtures15 ) ranging
from pH = 1,81 to pH = 11,98. The stock solution of the nitroparaffins
was 0,01 m. in 30 0/0 pure methanol; 1 ml of this stock solution was
usually mixed with 9 ml of the buffer, so that the solution used for
polarographic analysis was 0,001 m. The value of pH was checked by
the universal indicator of F. Cli ta and IL I{arnen. 16 ) Air was driven
out of the solutions by bubbling pure nitrogen.
*) The details of these preparations are given in the Czech publication quotl ld
above .

(;22 --

Experirnental results.

In strongly acidic solutions the polarographic curves of aJl nitropa l'affins here investigated show a well -developed wave (Fig. 1) with the
half-wave potential of about - 0 ,7 V (frolll the satur. KGl calolllel electrode), the height of which increases linearly with the concentration of
the llitrucompound. Big. J. also shows that the diffusion current diminishes as the lnolecula'r weight increases . Further, beginning frolH the
1JH = 4,5 onwards a new wave appearH at abouti - 1,5 V, which at
greater acidities is lua-skeel by the hydrogcll\.vave (Fig. 4). At still
greater pH valueH the second wave gradually diminishes until it disappears entirely. fn alkaline solutions the first \\'ave also diminishes
j

i,'Ii:!IIIiiilliJi4'l,l

i
I

I
I

i
I

,1

I,

I :!

;'

,/
I~

Fig. I .
O,()()l

m. solllt,iom; of nitrornuthane, llitroet)hmw, L-llit'l'opropano at pH = l ,t'l.

fknsit. 1 : 200, 4 V il('CII.

hut dom; not decrease entirely to zero. Individual differences between

the half-wave potentials of nitroparaffins arc not marked, as seen
from the followin g table:
pH

(''':I. l V0 2

(/ 2

H 5 N0 2

n; -03H7NO~

--0 ,75

n:/2 -:--: --() ,73

nYt = - 0,09

3 , :~

--- O ,R ~

4,(;

---O,H5
-0 ,87
---0,89
-0,90
-- 0 ,91

- () ,8 3
- --0,83
--O,8{)

- 0,81
- 0,84
- 0,85

~ () , 8~

~O,88

I ,H

5,7
6,H

8,0

9,1

nY2

----=

II ,fi

0 ,90
0,00
-- -0 , 90

] 1,0

O,BO

JO,4

11,2

--

~ 0,9I

-0,92
-0, !l:-~

-- 62:3 --

The valuet; 8how a much 8maiJer shift due to one lJH unit than would
eOITespond to the value O , Of)~ V. expected for reven;ihle electro-reductions.
To determine the num bol' of eledrons involved in the reduction, the
height of the nitroparaffin wave \vas cOIllpared with that due to the
electroreduction of nml e ic acid, which is known to procced with two
ulectrons per rnolecu Ie and which has about the same dimensions
(and diffusion ('ow~tant) as the nitropal'aJtin.
" 11,51

! !

1 -

fa

Ib

-..J

O/f!..J

];~jg.

2.

]""ft: 0,001 m. suLution uf lliLl'Odhnne at pH =-- 1,81, repeated. Right: a) 0,001 m .

and b) 0,002 nL malc'in acirt s()lntion. SAllsit,. L : }flO . .i Ya eclt.

As shown in Fig. ~. the diffusion current uf 0,001 m. 8ulution of

llitroethane is practically identical with that of a 0,002 nl. maleic acid.
This indicates that each lnolecule of nitroethane takes up four electrons
in the reduction process. To investigate this process further , the ratio
I

tn /If log -;--~-. was rl.erived , which - aecording to J. Tom eR19 )

~d

--

should

0 ,059 V

be equal to - - - - , provided that the electrode procesi'3 is a reversible

J'

one. From the gl'aphicaJ representation the ratio is

for nitromethane
Ilitroethane
1-nitropropane
l -nitrobutane

119 mV
122

113

lOB

which is nHlCh greater than the theoretical value corresponding to

a. foul' electron process (14 ,[) m V). TheRe high vnJues show the irre -

624 -

versibility of the process. 20 ) The prinlary reduction product must be

the respective N-alkylhydroxylamine, according to the equation

R- N < g

+ 4 ~)-7

20" -1- RN (free radical);

imnlediately the anions of water, 0" , join the hydrions to fornl water
and the free radical RN gets attached to a hydrion fornling RNH+, i. e.
the cation of the al kyl' hydroxylamine.
The linear dependence of the diffusion current on the concentration
was tested with solutions of the different nitroparaffins and found to
hold for concentrations fronl 1,8 X 10- 4 to 10- 3 In. From such results
the ratio of the diffusion constants of the four nitro paraffins comes
Ollt to he 1: O.H:3 : 0,07: 0 ,(-)1') (Fig. :~) .
II

60

III
40

20

Fig. 3.
He ight of tlH-\ diffuf-.: ioll current (in mms) plotted against concentrat ion s of nitropfl.rftffins (in millimol Rp.l.) 1. Nitromethane, n. NitroothH,n0. TTL I-Nitr'Opropane.
Snn Ritiv. 1 : 1!50. 4 V aecu.

As to the appearance of the second wave , which is shown in weakly

acidic and neutral solutions, there is every reason to believe that it
is rlue to the two-electron reduction of the respective hydroxylamine
to the amine (Fig. 4).
The height of this wave is , in 11101'e acidic so lutions, exactly equal to
one half of the first one. ctnd rlecreases slowly as the pH gets nearer
to 10. This indicates , that the fornl of hydroxylamine which is reduced
here , is the cation of the base. i. e. RN H +. 'rh e reduction pro cess of the
second wave is thlls

RlVH '- +

:2 ) +

H + ---, RNH t

.vielcling the eatiun of the alkyl am ine. The reduction potential of the
lIndissociated amine is probably considerably more negative - if it iH
reducible at all - so that with increasing pI! values the RNH+-wave
js merely diminish ed, no other wave appearing at more negative po tentials.

625 -

That the second wave shown in weakly acidic solutions is really due
to the alkyl hydroxylamine has been proved by recording curves of
solutions containing in the corresponding buffer solutions only the
N-methyl-hydroxylamine as well as curves of solutions with the nitro -

;'
I

o,~
Fig. 4.
n,OOl m. C 2 H 5 N0 2 at pH

--=

6,80, 7,96, 9,15. Sensitiv. 1 : 200, 4 V accu .

methane to which the N-methyl-hydroxylamine was added. In both

cases the wave at - 1,5 V appeared increasing according to the concentration of the hydroxylalnine and of the nitroparaffin .

Fi g .5.

0,001 m. hydroxy lamine h y drochloride at pH = 3,3,4,6, 6,8 , 8,0, 9,1, 10,4, 11 ,9.
Sensitiv. 1 : 150. First three curveR begin at 1,0 V , n ext two at ],2 V, last two at,
1,4 V. 4 V accu.

A similar set of curves was obta ined with ordinary hydroxylamine r

NH2 .OH, itself. It gave \,ell defined waves of the following half-wave
potentials (Fig. 5):

pH - - 4,(i
fl.7

1 A()

--- 1,4 7

1,">2

-- LJiH V

IJll --- S,O

-- L,GH

D,2
10 ,4

- - 1 ,7 f)

OSCI:Uoljl'aph ic inuestljafio1l8. It has been point.ed out. above that the

c haracte r of the fin;t llitroparaffin wave is that of an irreversible pro cess. The osuillographie potential -time curveH point to the same con clusion . Fig. f3 fl h(}\\-s t.he cathodic kink on th e asce nding branch, but
no time lag on the deHcending (anodic) branch. The same figure was
obt.ained with a ll ot.her nitropal'affins in various solutions. Th e capillary
e lectrone here u sed was the strearning one and the alternating voltage
was of the r ectangular c ha,ra e ter. l~)

r
r
.J ~

Fig. 6 .

Fig. 7.

0 1:le illogmph ie p o t ent ial -t ime cm'vcHlw'

to an ac idi c acetate buf'fe r -Bolution of
pH = 4,62 containing 0,0025 m. nitl'n m etlwl1f' . Fr'('qu f'ney IiO c. p. s.

A " d e rivate" c w'vo (aga in st tin'le b ase )

due to an acidic solution containing
0 ,0025 m. nitrobenzene' and nitrome than e . Frequency riO c. p. s .

Of ~q)ecia l intel'c:.;t if:; th e " derivative curve " (dn l dt ~ t) obtained with
a solution conta ining in the acidic solution nitrobenzene and nitrornethane in the sam e-molar concentration. The d escending parts of the
cut-in (Fig. 7) show the velocity of rertuction , i . c. the rate of the
acceptance of e lectrons.21 ) Nitrobenzene , which is r eadily reduced (at
a considerably positive potential) has in the part of the curve which
is due to the exh a ust ion of nitrobenzene molecules during their re(luction t he ~ Iop e d 2 n /dl 2 four times steeper than ir-; the slope due to
the electroredu ction of nitrOlllethane. This suggest that all four electrons are a cq llired by the nitrobenzene Inolecule practically simultaneomdy, whcreaf:; in th e case of nitronlCthane they are accepted
succcRs ively. Th e difference of the readiness with which the electronic
pro cer-;8 t a kes place in th e e lectroreduction of nitrobenzene and nitrometha ne is alr-;o r-;hown by the ordinary polarographic current-voltage
cur ve obtained with the dropping mercury cathode (Fig. 8). Again

-- l:i27 -

the first (nitrobenzene) curve is nluch steeper than the second (at
a. lnore negative potential) due to the nitromethane. Yet the reduction

of nitromethane proceeds quickly enough to give a well developed

WAve when the strearning mercury cathode is used instead of the

Fig. 8.

Fig. 9.

Polnt'ographic current-voltage curve,

(ll)tainecl with thp dropping mercury
tn,thode, duo to all acidic solution conUlining 0,0025 m. nitrobpllzene and
nitrometharw. 8enRitiv. 1 : 200.

Current-voltage curve, obtained with

th(~ s treaming InerctH"y cathode, due to
an acidic solution containing 0,0025 m.
nitromeHmne . Sensitiv. 1 : 2000.

dropping one (Fig. 9). At this electrode, the surface of which is

changed very qnickly (200 times per sec) slow electrolytic processes
a,1'e shown indistinctly, giving a very small wave. The fact, that even
,a t this very quickly renewed lnercury surface a full si7.e wave is de -

jr."':II'~:. ~.d~~",atYb,J.~1 I
: '"' Jl

25"

J'

Fig. 10.
Polarographi,c ,vaves due to a 0,002 m. nitroethane solution of pH = 10,38 re( ~orded 1. 3 min. n,ft,er the preparation 2. 3. etc. after every 6 min. Sensitiv.
1 : 100, 4 V HCC U.

veloped even for the electroreduction of the nitrOlncthane, proves that

every molecule which touches the electrode surface is reacting, there
being no retardation caused by any sort of slackened kinetic process.

Behaviour in alkaline solutions. It has been pointed out above

t.hat the nitroparaffin wave dinlinishes in alkaline solutions; this is

628 -

evidently due to the tautomeric change of the nitroparaffin into the

aci-form, which is not reducible within the range of potentials available
by the buffer (down to - 2,0 V).
According to A. Han tzsch 22 ) nitro paraffins containing a primary
or secondary nitrogroup fornl salts with alkalies derived from the.
aci-form

R- CII =N:<zr

The reaction velocity of this tautomeric

change depends on the pI! value of the solution. By chosing a suitable

pH value - between 7 and 8 - the rate of tautomerisation may be
followed very conveniently in registering, from time to time, the
height of the nitroparaffin wave (Figs. 10 and 11). It is significant
80

60

20

Fig. II.
Tho heights of waveR in mms (according to Fig. 10) plotted against the time after"
adding t,ho nitroethane to tho buffer solution of pH = 10,38.

that the height of the nitroparaffin wave does not fall to zero , but
remains constant at a sman value, when an equilibrium state is reached.
This evidently takes pJace when the acid-anions are in equilibrium with
the nlolecules. If at thiR state the acid cOlnponent of the buffer is
added , the nitro paraffin wave increases again to reach a final value corresponding to the adjusted pH-value. A detailed study of the kinetics
of this proto tropic change will be treated in a subsequent paper.
The author wishes to acknowledge his indebtedness to the Cze choslovak National R 3search Council for a grant and to Professor
J. Heyrovsky for his encouraging interest.
Summary.
The electroreduction of nitromethane, njtroethane, I-nitropropane,
and I -nitrobutane was studied polarographically in buffered solutions
of various pH -values. In strongly acidic solutions only one wave is
shown , due to the reduction of the nitro paraffin to the respective

.0

62!) -

A (I,Lkyl-hydroxylamine; in weakly acidic solutions 11 second wave

appears, around - 1,5 V , due to the reduction of the hydroxylalnine
cation to the corresponding alkyl alnine. In weak-Iy alkaline solutions
there is a gradual diminution of the paraffin wave with time, leading
to a certain constant small diffusion current; this change is due to the
rate of the tautomeric change of the molecular form to the anion form
of the pseudo-acid, which is not reducible within the range of potentials available.
The shape of the current-voltage curves indicates an irreversible
dectrode procegs and the same has been ascertained by oscillographi c
potential -time curves.
The Department jor general experimental organic Chemi8try
01 the Czech Institute of Technology (Geslce vysolce u,ceni techniclce) ,
Prague.

Li tera ture.
1) F.

Haber, Z. Elektrochem. 4 (1898) 511; Z. physik. Chom ie 32 (1900) 271.

2) Fr. Fich tel', Organische Elektrochemie , 1942, Dres(len u. Leipzig (Stein -

kopff).
3) M. Shikata, Trans . Faraday Soc. 21 (1925) 42; Mem. Coil. Agric., Kyoto
Imp. Unlv., Nr. 17 (1931).
4) I. M. Kolthoff and J. J. Lin gane, Polarography, 1941 , New York, p. 3R4.
5) J. Heyrovsky, Polarographie, 1941, Wien (Springer).
6) Th. de Vries and R. W. Iw e tt, Ind. Eng. Chern., Anal. Etl.13 (1941) 33~L
7) P. Pierron, Bull. Soc. Chim. Franco, [3],21 (1899) 780.
8) ChI'. Grundmann, Chemi e 56 (1943) 165; Bel'. 77 (1944) 82. Fr. AKill gt'l', Bel'. 77 (1944) 73.
Y) Organische Synthesen, p. 400.
10) V. Aug e r, Bull. Soc. Chim. France , [3], 23 (1900) 333.
11) R. B. R e ynolds and H. Adkins, J. A. C. S. 51 (1929) 279.
12) J. Mei se nh e im e r amI Liang-Han-Chou, Annalen 539 (1939) 84 .
19) J. Heyrov s ky, Polarographie, p. 223.
14) J. Heyrov s ky and J. Forejt, Z. physik. Chem. 193 (1943) 77 . ,T. H e r rovsky, F. 80rm and J. For e jt, Collection 12 (1947) II.
15) H. T. S. Britton, Hydrogen Ions , 1932, p. 225.
16) F. Cuta and K. Kamen, Collection 8 (1936) 395.
17) J. Heyrovsky, Polaro~raphie, p. 83.
18) E. Vopicka, Collection 8 (1936) 349.
19) JO
. Tomes, Collection 9 (1937) 12.
20) 1. M. Kolthoff and J. J. Lingane, Polarography, p. 195.
21 ) J. Heyrovsky, Chern. listy 40 (1946) 229.
22) A. Han tzsch, Bel'. 32 (1899) 575.
42