06 Chapter1
06 Chapter1
06 Chapter1
CHAPTER 1
INTRODUCTION
1.1 HYDRAZINE
1.1.1 Applications
high heats of combustion. They have nitrogen in -2 valence state. Nitrogen's natural
tendency, however, is towards zero valency (N ≡ N), which gives off nearly six
times as much as energy as the N-N bond. Thus tremendous amount of energy is
released not only during decomposition of N2H4 to N2 but also at the time of the
mixing with the oxidizer. Hence they are used as fuels in rocket and spacecraft
powered engines. As a strong reducing agent, hydrazine is used for corrosion control
in boilers and hot water heating systems, for metal plating, and for reducing noble
metal catalysts and unsaturated bonds in organic compounds. It is also an oxidizing
agent under suitable conditions with two active nucleophilic nitrogens and four
replaceable hydrogens. It is the starting material for many derivatives; among which,
foaming agents for plastics, antioxidants, polymers, polymer cross linking and chain
extending agents, as well as biologically active pesticides, herbicides, plant growth
regulators and pharmaceuticals are important. As it is a good complexing ligand,
numerous complexes have been studied (Bottomley 1970 and Schmidt 1984). Many
heterocyclics are based on hydrazine, with rings containing from 1 to 5 nitrogen
atoms as well as other hetero atoms. The many advantageous properties of hydrazine
are exploited in the field of photographic chemicals and dyes. New uses for
hydrazine derivatives are discovered daily.
In principle, it can form two series of salts with monobasic acids, one
having the hydrazinium (+1) cation, N2H5+ and the other, hydrazinium(+2) cation,
N2H62+. The basic ionization constants of hydrazine in water suggest that N2H62+
exists only in the solid state or in conc. acid solutions. The salts containing this
cation are extensively hydrolyzed in water to give highly acidic solutions containing
the N2H5+ ion.
Hydrazine forms not only mono- and di acid salts of the types, N2H4·HA,
N2H4·2HA where HA represents a simple mono-basic acid, but also compounds of
the types 2N2H4·H2B and N2H4·H2B where H2B represents a dibasic acid. The best
known of these are N2H4·HA or 2N2H4·H2B [N2H5A or (N2H5)2B] and N2H4·2HA or
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N2H4·H2B [N2H6A2 or N2H6B] and not N2H4·2H2B. The N2H5+ and N2H62+ salts are
generally referred to as hydrazinium(+1) and hydrazinium(+2) salts respectively.
Even though N2H62+ salts are generally formed with strong acids, double
salts of this cation with ammonium ion are also formed. For example,
(NH4)2N2H6(ClO4)4 and (NH4)2N2H6(SO4)2 (Frech et al 1993) salts have been
prepared and characterized. Recently redetermination of hydrazinium (+2)
dichloride (N2H62+.2Cl-) has been reported (Kruszynski and Trzesowska 2007). In
many cases the preparation of hydrazinium salts is very easy, but in other cases,
such as in the preparation of hydrazinium nitrates or perchlorates, special
precautions are necessary to prevent unexpected explosions.
where HA is a monobasic acid, e.g., HCl, CH3COOH, HNO3 etc. and H2B is a
dibasic acid, e.g. H2SO4, H2C2O4 etc.Acids like H2SO4 (Hudson et al 1967) and HF
(Patil et al 1979) react with N2H4.H2O to form exclusively N2H62+ salts because of
their strong acidic nature and the low solubility of the resulting salts.
1.2.1.2 Double Decomposition Method
salts N2H4·2HA (N2H6 A2). Again N2H5+ salts are mostly hygroscopic and even some
of them are in liquid state (Patil et al 1980), while N2H62+ salts are not so, with an
exception of N2H6(ClO4)2.2H2O which is highly hygroscopic.
Hydrazine hydrate reacts with halogen acids to give salts of the type
N2H5X and N2H6X2 under different reaction conditions (Patil et al 1979, Patil et al
1978), where X = Cl-, Br-, I- or F-. When pure hydrazine reacts with nitric acid it
forms hydrazinium (+) nitrate and its crystal structure is reported (Grigoriev et al
2005). Hydrazine and nitrous acid undergo mutual destructive reaction. In neutral
solution it is possible to obtain hydrazinium(+1) nitrite as colorless to yellowish
hygroscopic solid.
The latter salt also forms 1:1 adduct with phosphoric acid: N2H5H2PO4
.H3PO4. The salts N2H5H2PO4 and (N2H5)2HPO4 have been prepared by the reaction
between the corresponding ammonium phosphate and hydrazine hydrate and
characterized (Patil et al 1978) by chemical analysis and IR spectra(νN-N = 980 cm -1).
like pyridine dicarboxylic acids (Saravanan and Govindarajan 2003) and pyrazine
carboxylic acids (Premkumar et al 2003) have been prepared by the acid-base
neutralisation method and characterized. Hydrazine also forms salts with aromatic
carboxylic acids like benzoic, salicylic, phthalic acids (Kuppusamy 1995), trimesic,
trimellitic, hemimellitic and pyromellitic acids (Vairam and Govindarajan 2004),
naphthoic, hydroxy naphthoic and naphthoxy acetic acids (Arunadevi 2009).
The hydrazinium salts of the type N2H5X [X = Cl-, Br-, I-, 0.5SO42-,
H2PO4-] decompose exothermally in air to the corresponding ammonium salts with
the evolution of ammonia and nitrogen (Patil et al 1979 and Jasim 1988). Some of
the hydrazinium salts like N2H5N3 (Patil et al 1979), N2H5HF2 (Patil et al 1979) and
N2H5F (Soundararajan 1979) do not decompose exothermally, but volatilize under
the conditions employed. The simultaneous TG, DTA and EGA thermolysis of
hydrazinium sulphate has also been studied (Jasim 1988). The hydrazine salts such
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Mahesh and Patil 1986) are the usual products of reaction between hydrazine
hydrate and first row transition metal salts.
1.4.2.4 Reactions of Hydrazine Hydrate and the Acid Mixture with Metal
Salts
al 1982). This phenomenon has been made use of in the preparation of fine particle
ferrites (Gajapathy and Patil 1983) and cobaltites (Patil et al 1983) by the low
temperature decomposition of M1/3Fe2/3(C2O4)(N2H4)2 (M = Mg, Mn, Co, Ni or Zn)
and M1/3Co2/3(C2O4)(N2H4)2 (M = Mg or Ni), respectively. Large surface area CeO2
has been prepared by the thermal decomposition of cerium oxalate hydrazine
complex. The thermal behaviour of metal maleate and fumarate hydrazine
complexes have also been reported (Govindarajan et al 1995). The decomposition of
nickel hydrazine glycinate complexes (Sivasankar 1994) have been reported to be
violently exothermic and lead to explosion if the samples are heated in bulk. They
give metal powder as the final product, even in air, unusually. Metal (Co, Ni and Zn)
hydrazine phthalate complexes produce metal powder and benzoate, isophthalate
and terephthalate complexes, the oxides as residue (Kuppusamy 1995).
Metal hydrazine carboxylates decompose in air at a low temperature (75-
200°C) to yield fine particle oxide materials. Thermal studies on
M(N2H3COO)2.nH2O, (M = Ca, Mg, Mn, Fe, Co, Ni, Zn or Cu; n = 0, 0.5, 1, 2, 3)
are carried out extensively in air or inert atmosphere (Ravidranathan and Patil 1985,
Macek and Rahten 1989, Macek and Rahten 1993, Braibanti et al 1967, Manoharan
and Patil 1989). The thermal property of Nd(N2H3COO)3.3H2O in an inert
atmosphere, (Macek and Rahten 1989, Macek and Rahten 1993) the synthesis of
La(N2H3COO)3.2H2O and, thermal reactivity of Ln(N2H3COO)3.3H2O,(Ln = Ce, Pr,
Nd, Sm, Eu, Gd, Tb, Dy, Ho, Er, Yb or Y) and UO2(N2H3COO)2N2H4.H2O
(Mahesh et al 1986) have been reported already. The decomposition is autocatalytic
and accompanied by swelling due to the evolution of large amounts of gases like
NH3, H2O, H2 and CO2. The preparation of γ-Fe2O3 and Co doped γ-Fe2O3 the
commonly used recording material has been achieved by the thermal decomposition
of iron hydrazine carboxylates in a single step. Similarly ultra fine ferrites and fine
particle cobaltites have been obtained at very low temperatures by the thermal
decomposition/combustion, of solid solution precursors (Ravindranathan and Patil
1987, Arunadevi et al 2009).
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Slivink et al, 1968 and others have studied the thermal decomposition of
N2H5+ and N2H62+ fluorometallates of transition metals (Frlec et al 1980, Frlec et al
1981, Slivnik et al 1966, Siftar and Bukovec 1970 and Bukovec et al 1971). The
intermediate products of thermal decomposition are either hydrazinium(+1)
fluorometallates, which further decompose to ammonium fluorometallates or
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formation of the metal oxides as the final products of decomposition. However, the
authors (Macek and Rahten 1989 and Macek and Rahten 1993) who experimented
the thermal decomposition in argon atmosphere for Fe, Co and Ni complexes have
reported the metal powders as the end products, which are very reactive and
sensitive to oxidation by the impurities in the argon. All of them decompose
exothermally.
Braibanti et al, 1968 have given a thumb rule on the basis of earlier
studies. In the complexes examined by them and others, νN-N could be found at the
following frequency ranges:
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Although the N-N stretchings for free N2H5+ and bridging N2H4 overlap,
fixing the molecular formulae can identify them by analytical and other techniques.
Figure 1.1 The possible isomers of hydrazine (a) Staggered trans C2h
(b) Eclipsed cis C2v (c) Semi-eclipsed half cis C2 (d) Gauche C
considered to be the equilibrium conformation as both the eclipsed and the semi-
eclipsed conformations would involve coplanar repulsions.
(ii) Salts of hydrazine with HCl, HF, HBr, H2SO4, HCIO4, H3PO4,
H2C2O4.2H2O, CH3COOH, 2, 3 pyrazinedicarboxylic acid, 3, 5-
pyrazoledicarboxylic acid etc.
Extensive work has been done by Liminga and his coworkers (Liminga
and Olovsson 1964, Liminga and Alex Mehlsen 1969 and Liminga 1967). The
crystal structure of N2H5+C4H5O6- consists of infinite chain of tartrate anions linked
by head to tail by O – H…O hydrogen bonds. Two such chains are cross-connected
by O – H....O hydrogen bonds to form dimeric chains. The hydrazinium cation sits at
the center of four tartrate dimers and bridges them by two center and three center N -
H....O hydrogen bonds. As a whole, the structure is stabilized by numerous hydrogen
bonds.
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NH2
NH2 H
O
C NH2 N
O
M
O C
N NH2
NH2 O
H
NH2
Many stable complexes of metal salts with one, two or three hydrazine
molecules are known, but their structures have so far received very little attention.
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The only available crystal structures are on the complexes M(N2H4)2X2 (Ferrari et al
1963 and Ferrari et al 1965) (M= Mn, Co, Ni, Zn or Cd and X= Cl- (Ferrari et al
1963), NCS- (Ferrari et al 1965) and CH3COO- (Ferrari et al 1965). The above
complexes have infinite chain structures (Figure 1.3) with cis bridging hydrazine
molecules and respective anions in the trans positions.
X X
NH2
NH2 NH2 NH2
M M
X X
Figure 1.3 Structure of [M(N2H4)2X2]n where M= Mn, Co, Ni, Zn and Cd; X=
Cl-, NCS– and CH3COO–
It has been pointed out that chains of complexes are not held together by
hydrogen bonds, thus favouring twinning which is observed in the crystals.
2+
CH3
P
C
P NH2
Co
P NH2
+
NH3
S
S
C NH2
C
N N
Co
N N
C NH2 C
S NH3 S
+
2-
O O
C O O C
Cu
C O O C
O O
For clarity the structure of acids and the different coordination modes of
hydrazine are shown in Figure 1.8(a-d) and 1.9(a-c) respectively.
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SH-CHCOOH
SHCH2COOH COSH
CH 2 COOH
HO
O
HO
S
OH
O O
Based on the above objectives, this research work was performed and
the results obtained are discussed in the following chapters.