366 ANALYTICA CHIMICA ACTA

THERMAL ANALYSIS OF SOME METAL BEN%OHYDI<OXAMATES

LEONARD N. LAPATNICti, J. FREiXkH= EIA%15L AND WALLACE M. McNABR

Clrer,rislry Deparhnenl. Uttivcvsity of Pcn~~rsylvu~riu,Plriludcl~iria, Pa. (U.S.A.)
(Rcccivccl April rGth, rgG6)

Benzohyclroxamic acid (BHA, N-bcnzoylhydroxylamine) was first prepared

in 1872 by LossEN I. It has been used cxtensivcly in analytical chemistry as a colori-
metric reagent and as a precipitant, the principal applications being in the deter-
mination of va.naclium”-4, mangancsc6~0, molybclenum~, iron718, thoriumo, uranium”~io,
titaniumli, coppcrr”, cobalt’” and nickelis.
No reports on thermal analysis of BHA chelates have appeared in the literature.
The present paper deals with the differential thermal analysis (DTA) and thermo-
gravimetric analysis (TGA) of BHA and its precipitates with some common metals.
The precipitates studied were those with aluminum(III), caclmium(II), cobalt(II),
copper(H) (2 precipitates), iron(III), lantlnmum(III), leacl(II), manganese(II),
nickcl(II), uranium(V1) and zinc(I1).

The DTA and TGA apparatus has been described clscwhcrera~f4.

The7mal a9talysis firocedzcres

TGA was carriccl out at a heating rate of S”/min with samples of varying size,
clepcnding on the metal ion in the chelate. The thermobalancc was checkccl by deter-
mining the weight of residue in the crucible after a reasonable cooling period.
DTA runs were carried out using 30-30 mg of &elate for runs in oxygen,
about Go mg for runs in nitrogen. mixccl with enough r8o-mesh silicon carbide to
give about Goo rng of material in the sample block. About Goo mg of silicon carbide
was used as reference material. The covcrecl block was then hcatcd at P/mm at a
gas flow rate of about 20 nil/niin.

Pvepavation of chelates
A roughly weighed amount of BHA was dissolved in about IOO ml of water
containing 0.5 meq of perchloric acid. Enough metal ion solution was added to the
BHA solution to leave an excess of z5-50~/~ BHA. The resulting solution was treated
dropwise with I M sodium hydroxicle solution until precipitation occurred. When
the metal was non-amphoteric, base addition was continued until a PH of S-g was
attained. When the metal was amphoteric, the base was added until the precipitate
seemed to coagulate. The general reaction involved is:

Awal. Chim. Ada, 36 (x966) 366-371

THERMAL ANALYSIS OF BENZOHYDROXAMATES 367

TABLE I
ANALYSIS OF CHELATES

Cltelute 0/0 C talc. o/o c fourrd o/o H talc. O/JH fowd

AI(BHA)s - g.HaO 54.55 54.0= 4.58 4.53

Cd(BHA)a - jCHz0 42.23 42.23 3.42 3.48
Co(BHA)a * Hz0 48.15 48.20 4.04 4.05
Cu(BHA)r 50.20 SO.53 3.Go 3.74

Cu(BHA)a * )X&O 49.42 49.62 3.70 3.G2

Fc(BHA)a - Hz0 52.30 52.02 4.18 4.82
La(BHA)s * He0 44.62 44.53 3.57 3.39
Pb(OH)a* 4Pb (BHA)a 31.16 31.89 2-33 2.54

;Lln(BHA)2 * &Hz0 50.02 50.07 3.90 3.78

Ni(BHA)n - Hz0 48.18 48.13 4.04 4.21
UOa(.w-KA)a 31.01 31.03 2.23 2.22
%n(BH& - Hz0 47.28 47.52 3.97 4.12
---__ .._.._.-.- _._____,__ --- -__-_ ------_--_--._ _ --_--

Fig. I. DTA curves in 02.

Fig. 2. DTA curves in N2.

Anal. Cltim. Ada, 36 (x966) 366-371

 I.. N. LAPATNICK, J. P. HAZEL, W. M. MCNABB
368

OH
II I
MR.++ 9% -C-N-OH + xHz0
0\ / 0 H
il I
3 M( \ ,---.C-N-O),.xHzO + lzH+
0

When the metal ion was lead(H), it seemed that hydrolysis could not be prevented
with the cxccss of BHA used in these experiments. When mangancsc(I1) was the
metal ion, IO ml of IO/~ hydroxylammonium chloride solution was used to prevent
the oxidation in basic medium of manganese(I1) to manganese(III)s. The reducing
agent must be added before base addition is begun.

RESULTS AND DISCUSSION

Under the uncontrolled conditions used here, only nickel(II), cobalt(H),

--
EHA
\

Fig. 3. TGA curves in 00.

Fig. 4. TGA curves in ND.

Anal. Chim. Acta, 36 (1966) 366-371

THERMAL ANALYSIS OF BENZOHYDROXAMATES 369

copper( cadmium(I1) and lanthanum(II1) were definitely precipitated quantita-

tively. The copper(I1) began to precipitate as soon as the metal ion solution was added
to the acidic BHA solution. This precipitate was found to be different from that ob-
tained by addition of base until a pH of S-9 was reached. The precipitate formed in
the latter case was dark green and analyzed as Cu(BHA)a - &HaO. The other precipitate
was blue-green in color and analyzes as Cu(BHA)z.
No mention is made in the literature of precipitation of aluminum(III),
lead(H), lanthanum(II1) or manganese(I1) with benzohydroxamic acid. The precipi-
tate of each of these metals is, therefore, a new compound. Table I lists the carbon
and hydrogen analyses for each of the chelates.
The DTA curves of the chelates and of BHA in oxygen and in nitrogen and
the corresponding TGA curves are shown in Figs. 1-4. There seem to be no common
features in the set of curves. Some of the chelates decompose exothermically, others

TABLE II
HRATS OF DECOMPOSITION FOR hIETAL CHELATES

Ckclate Satnple weight A vea Heat evolved Heat of decomp.

(VW or absorbed (kcaljnrole)
(cal) (call&
.________~___ _-
A~(BHA)J* 1 Ha0 52.G 268 -9.59 - 182 -84.1
47.5 250 -8.93 - x88 - 87.0

Cd(BHA)a.3 Ha0 64.5 182 4.30 66.7 26.5

6G.2 ‘84 4.36 65.8 26.2

Co(BHA)a.HaO 61.8 139 3.75 60.7 2x.2

64. I 139 I 3.75 58.5 20.4

Cu(BHA)a 38.6 241 -7.50 - 194 - 65.2

40.2 255 -7.92 - 197 -66.5

Cu(BHA)a.$HaO 71.8 256 -8.12 - XI3 - 38.4

64.6 220 - 6.98 - 108 - 36.8

Fc(BHA)a.HaO 37.8 191 -7.32 - 194 -93.5

41.3 204 - 7.81 - 189 -gx.r

La(BHA)a.HzO 81.8 25 -0.64 -7.8 -4.4

97.5 29 -0.74 -7.6 -4.3

Fb(OH)a-4l’b(BHA)a 99.0 I q.02 0.2 0.4

94.6 I 0.02 0.2 0.4
Mn (BHA)a**HaO 28.7 1.27 44.3 X4.9
36.5 z; x.69 46.4 X5.6

Ni( BHA) a* Ha0 60.7 26 0.8x X3.3 4.6

75.2 31 0.97 12.9 4.5

UOa(BHA)a 52.6 378 - 14.8 - 281 -x52

49.7 363 - 14.2 - 286 -155

Zn(BHA)a- Ha0 62.2 239 6.45 =o4 37.0

63.8 258 6.95 109 38.7
BHA (fusion) 67.9 I.49 21.9 3.0
65.1 1.38 21.2 2.9
BHA (decomposition) 67.9 1255 - 28.7 - 423 - 58.0
65.1 1x81 - 27.0 -415 - 56.8

Anal. Ckirn. .ic:~, 36 (ryGG) 366-37:

370 L. N. LAPATNICX, J. P. HAZEL, W. M. MClvABB

endothermically. No single factor can be used to explain the relative heats of de-
composition, although the fact that benzohydroxamic acid itself decomposes exother-
mically indicates that, in the absence of other complications, the compounds should
all decompose exothermicall_y. Table II summarizes the heat of decomposition
results, while Table III lists the attempts to correlate the heats of decomposition
with other parameters.

TABLE III
PROPERTIES USED IN ATTEMPTS TO CORRELATE TII&RhIAL ANALYSIS DATA
_- .__..._- ___-___-_ ...-- --- ~____..._.___. _ .___ . ____ ----.
I-icd of decornposilion
U03(BHA)2 > Fe(RHA)a* Hz0 > AI(BHA)a.QH30 > Cu(BHA)a >
CU(BHA)~~)H~O > La(BHA)aeHzO > Pb(OH)a.qPb(BI-IA)z > Ni(BI-IA)~*HzO >
.Mn(BI-Ih)~~~HzO > CO(BHA)~~I-I~O > Cd(BHA)~~~H~O > Zn(BIih)a-I&O

Tcnt~erittaire of DTA decowposilion peal6

UOa(BI-IA)z> hl(l%-IA)g. ~1-120 > C~I(BI-IA)~~)H~O > Cu(BHA)-, = Ni(Bl-iA):!.H& >
I~c(BHA)n~I-I20 > Zn(I~HA)~~11,0 = Co(BHA)o*H,O > La(BHA)n.HaO >
Cd(J3HA)~~,~H~O > Mn(l3I-Ih)~~&F-I~O > Pb(OI-I)~~~I~b(BI-IA)s

[Zeul of forttiatiou of ruclnl oxide

1JaOs > La303 > AhOn > ITca03 > Co304 > MnOz > ZnO > Cd0 >
NiO > PIJO > CuO

Radius of corlral ion

Pb3.b > T.nn+ > Ccla+ > Mn?+ > %nz+ > Co2+ > Cu3+ > Ni”+ > Fc3+ > Ala+

Clravge-lo-radifrs rdio of ccnlrnl ion

Aln+ > Fc3.k > Ni*+ > Cu3+ > CO~+=L;L~+ > Znz+ > Mnz+ > Cdz+ > Pb=+

Pb(OM)3.@‘b(Bl-iA)* > La(BHA)~~H-,O > UOs(BI-IA)c > Fc(BHA)3*HzO >

Al(BNA)~*#I-110 > Ccl(BI-IA)~~~1-I~O > Zn(BI-IA)3.Hr0 > Co(BHA)a*HzO >
Ni(BHA)a*HaO > C~(BHA)~*+HIO > Mn(BI-?A)~~&I-&O > Cu(BHA)z

nI0h ficrcenl waler

hl(BHA)3 * 4) HoO>Co(BHA)a . Hz0 = Fc(BI-IA)=. He0 = Ln(BHA)a . Hz0 =
Ni(BHA)z e I-I30 = Zn(BHA)a - HaO>Cd(BNA)~ - 2 H30>Mn(BHA)a - 4 l&O>
Cu(BHA)3 )HgO>
l Pb(OH)s . 4l?b(BH_Qa>Cu(BMA)3 = U03(BHh)~
_-- ------ _-_-____-_-

The heats of decomposition of the chelates and of BHA and the heat of fusion
of BHA were estimated from the areas under the peaks of the DTA runs in nitrogen.
The following equation was used for this estimation. Heat per unit area (calories) =
afb (t- 129, where a and b are constants which depend on the amplifier range
used in the run, and t is temperature (“). The equation is derived by using the known
heats of fusion and the measured areas of the fusion peaks of samples of anthracene
(apparent m.p. 220~) and of benzoic acid (apparent m.p. 1257, and assuming a linear
relationship between temperature and heat change per unit area.
.
at 2000 pV, a = 2.71. xo-o, b = 1.87.10-4 ‘.
at 1000 pv, a = 1.95. x0-2, 2i= 1.36. x0-4
Some of the products of the thermal decomposition have been identified as
benzonitrile, metal benzoate, metal oxide, aniline, benzamicle, carbon dioxide and
tars.

Anal. Chim. Ada, 36 (1966) 366-371

THERMAL ANALYSIS OF BENZOHYDROXAMATES 37=

In the one instance where a comparison can be made of the heat of decom-
position of a BHA chelate and a BPHA (N-benzoyl-N-phenylhydroxylamine. N-
phenylbenzohydroxamic acid) chelate, the decomposition of Cu(BPHA)z is more
exothermic than that of CU(BH*A)Z.
The copper chelates were found to be soluble at PH II, and the application
of this property to the separation of copper from some other metals is now being
studied.
A study of the use of the lanthanum, cadmium, copper, nickel andcobalt
chelates as analytical precipitates is planned.

The preparation and thermal analysis of metal chelates of benzohydroxamic

acid (BHA) with Al(III), Cd(II), Co(H), Cu(I1) (two compounds), Fe(III), La(III),
Pb(II), Mn(II), Ni(II), U(VI) and Zn(I1) is discussed. The Al(III), La(III), Pb(I1)
and Mn(I1) chelates arc new compounds. DTA and TGA curves of the chelates and
of BHA arc presented, and the heats of decomposition of the chelates are estimated.

Les auteurs ont effect& une etude sur la prdparation et l’analysc thcrmiquc
de chdlates m&alliques de l’acide benzohydroxamique (BHA) avec Al, Cd, Co, Cu,
I;e(III), La, Pb, Mn, Ni, U et Zn. Lcs chelates dc Al, La, Ph et Mn sont de nouveaux
composds. On donne des courbcs de ces chelates ainsi que les chaleurs de d&composition.

Die Hcrstellung und thermische Analyse der Metallchelate von Benzohydrox-

amsiure (BHA) mit Al(III), Cd(II), Co(II), Cu(I1) (2 Verbindungen), Fe(III),
La(III), Pb(II), Mn(II), Ni(II), U(V1) und Zn(II) wird diskutiert. Die Al(III)-,
La(III)-, Pb(II)- und Mn (II)-Chelate sind neue Verbindungen. DTA- und TGA-Kurven
der Chelate und des BHA werden angegeben und die Zersetzungswirmen der Chelate
abgeschatzt.

REFERENCES

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Anal. Cihn. Acta, 36 (1966) 366-371