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CHAPTER 1
INTRODUCTION
1.1 HYDRAZINE
group. The hydrated hydrazine, N2H4.H2O was first prepared by Curtius in 1887. The
anhydrous hydrazine as a water free base was prepared by De Bruyn for the first time.
1.1.1 Applications
surprisingly stable in view of its endothermic nature(∆H f = 50.43KJ /mol) and its
simple methyl and dimethyl derivatives have endothermic heats of formation and
2
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.
the more electronegative group NH2 has the - I effect on the lone pair of electron of
the neighbouring nitrogen, making it less basic for protonation.
+
NH3 + H2O → NH4 +OH- Kb =1.8 X 10-5 (1.1)
+ - -7 (1.2)
N 2 H 4 + H2 O → N 2 H 5 +OH Kb = 8.5 X 10
3
+ 2+ - -16
N2H5 + H2O → N2H6 + OH Kb = 8.9 X 10 (1.3)
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.
2+ + +
N2H6 + H2O → N2H5 + H3O (1.4)
The divalent cation seems to violate Pauling’s adjacent charge rule, H 3N+-
+ +
NH3 , but is likely that this is in equilibrium with other tautomeric forms, e.g. H 3N -
NH2H+.The N2H5+ salts have been prepared with carboxylic acids and numerous
2+
examples of them have been reported (Schmidt 1984), whereas the salts of N 2H6 are
limited (Starosta and Leciejewicz 2007, Starosta and Leciejewicz 2008).
Hydrazine forms not only mono- and di acid salts of the types, N 2H4·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
4
+ 2+
N2H4·H2B [N2H6A2 or N2H6B] and not N2H4·2H2B. The N2H5 and N2H6 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,
where HA is a monobasic acid, e.g., HCl, CH 3COOH, HNO3 etc. and H2B is a dibasic
acid, e.g. H2SO4, H2C2O4 etc.Acids like H2SO4 (Hudson et al 1967) and HF (Patil et
2+
al 1979) react with N2H4.H2O to form exclusively N2H6 salts because of their strong
acidic nature and the low solubility of the resulting salts.
1.2.1.2 Double Decomposition Method
2- 2- 2- 2-
where Y = SO4 , C2O4 , HPO4 , S2O3 etc.
monoacid salts N2H4.HA [N2H5A] are usually more soluble in water than the diacid
6
+
salts N2H4·2HA (N2H6A2). Again N2H5 salts are mostly hygroscopic and even some
of them are in liquid state (Patil et al 1980), while N 2H62+ 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.
(N H ) H P O
2 5 3 2 3 10
were prepared
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(ν N-N = 980 cm-1).
been prepared by mixing hot aqueous solutions, whereas (N2H5)2C2O4 has been
prepared in cold condition. Efforts to crystallize the latter from hot solution always
resulted in the former only.
Numerous salts of hydrazine with several organic acids are available in the
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
10
The hydrazine does not frequently act as a reducing agent in reactions with
transition metals but acts as a ligand to form complexes. This broad area of hydrazine
complexes has been reviewed earlier (Bottomley 1970, Dilworth 1976).
+
Monoprotonated hydrazine, hydrazinium cation (N2H5 ) still retains a basic
site and is capable of coordination. It is potentially a monodentate ligand and
complexes containing it are known. The donor abilities of hydrazine from
complexometric titration (Bisacchi and Goldwhite 1970) are shown in the order:
2- 2- - -
where X = 0.5 SO4 , 0.5 C2O4 , N3 , ClO4 etc.
Mahesh and Patil 1986) are the usual products of reaction between hydrazine hydrate
and first row transition metal salts.
(Sivasankar and Govindarajan 1994, Patil et al 1983 and Sivasankar and Govindarajan
1995).
The hydrazinium (+2) metal complexes have also been isolated and studied
(Glavic et al 1975, Slivnik et al 1968, Frlec et al 1980). The hydrazinium (+1)
lanthanide metal sulphate complexes have been prepared by the reaction between the
lanthanide salts and N2H6SO4 and studied systematically (Bukovec and Miliev 1987
and Govindarajan et al 1986).
1.4.2.4 Reactions of Hydrazine Hydrate and the Acid Mixture with Metal
Salts
Instead of hydrazinium salts, the mixture of hydrazine hydrate and the acid
of the corresponding anion can be added to the metal salt solution which precipitates
solid form. A report describes the preparation of MX(N 2H4)2 (M = Co, Ni, Zn or Cd ;
X = malonate or succinate) complexes by adding a mixture of hydrazine hydrate and
the acids to the metal nitrate hydrates (Sivasankar and Govindarajan 1994).
(N2H5)2UF6 has been prepared by the reaction between UF6 and N2H5F in anhydrous
hydrazine (Glavic and Slivnik 1970). The lanthanide hydrazine complexes with anions
like halides, carbonate, nitrate, sulphate, perchlorate, acetate, oxalate (Schmidt 1984)
and squarate(Vairam and Govindarajan 2006) have been prepared by the addition of
hydrazine hydrate to the metal salts in an aqueous or alcoholic medium.
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
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).
19
Slivink et al, 1968 and others have studied the thermal decomposition of
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.
One of the best features of an infrared spectrum is that the absorption or the
lack of absorption in specific frequency regions can be correlated with specific
stretching and bending motions and in some cases, with the relationship of these
groups to the remainder of the molecule. IR spectra of hydrazine and its derivatives
-1 -1
are studied in the finger print region between 1300 cm and 650 cm . They have
been reported for several hydrazine derivatives (Savoie and Guay 1975, Glavic and
Hadzi 1972) and metal complexes (Nieuwpoort and Reedijik 1973, Brown et al 1979,
Braibanti et al 1968). Normal coordinate analysis for N 2H2, N2H4, N2H5+, N2H62+ has
been carried out (Mielke and Ratajczak 1973).
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:
22
-1
N2H4 (in solid state) 875 cm
N2H4 (unidendate) 930-940 cm-1
N2H4 ( bridging ) 948 - 985 cm-1
NH2NHY (Y = COO, CSS) 986-1012 cm-1
+
Although the N-N stretchings for free N2H5 and bridging N2H4 overlap,
fixing the molecular formulae can identify them by analytical and other techniques.
The assignment of the band at 875 cm-1 in the spectrum of hydrazine to νN-
N was questioned by Durig et al (Durig et al 1966), who assigned this band to - NH 2
rocking vibration and the band at 1126 cm-1 to νN-N. The infrared spectra of
M(N2H4)2Cl2 (M = Mn, Fe, Co, Ni or Zn) complexes were recorded (Satyanarayana
and Nicholis 1978 ) and the absorption in the region 1150 -1170 cm -1 were assigned to
νN-N of bridged hydrazine. Despite these reservations, the frequency of ν N-N is a
useful indication of the type of coordinated hydrazine.
23
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.
Electronic, infrared, Raman and microwave spectra show that the molecule
has C2 symmetry in the vapour and liquid states (Durig et al 1975). However, X-ray
and neutron diffraction investigations in the solid state show that the molecule to have
either the gauche (C2) or cis (C2V) conformation.
(ii) Salts of hydrazine with HCl, HF, HBr, H 2SO4, 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
....
NH2
H
O NH2
NH2 N
C O
N NH2 O C
H NH2 O
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.
26
The only available crystal structures are on the complexes M(N 2H4)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 CH 3COO (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
M M
NH NH2 NH NH2
2 2
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
NH
P 2
octahedron made up of two nitrogen atoms (one from each N 2H5+ ion), two oxygen
atoms(from water molecule) and two chlorine atoms. The complex is found to be
isomorphous with the corresponding Co, Ni and Cu analogues.
+
NH
S 3
S
NH
C 2 C
N N
Co
N N
C NH2 C
S NH3 S
+
Though N2H5 ion is a potential coordinating group, in some compounds it
behaves like the ammonium ion, i.e. it is outside the coordination sphere. The
compounds with halides and hydrazinecarboxylate anions fall under this category.
has N2H5+ cation, complex anion and water molecules. In the complex anion, the
nickel(II) is octahedrally coordinated by three bidentate hydrazine carboxylate anions.
The crystals of the nickel compound, (N2H5)[Ni(N2H3COO)3].H2O are piezoelectric.
The corresponding cobalt and zinc compounds are isomorphous with the nickel
compound (Jesih et al 2004). A novel coordination mode for hydrazine carboxylate in
a polymeric, ten-coordinate barium complex has been established crystallographically
(Edwards et al 1993).
The crystal structure of N2H5[Cu(C2O4)2].H2O (Gajapathy et al 1983) has
revealed that the molecule contains discrete N2H5+ ions, [Cu(C2O4)2]2- ions and water
molecules. It is shown in Figure 1.7. The same authors have reported the non-
coordination of N2H5+ in (N2H5)2Co(C2O4)2.3H2O.
31
2-
O
O
C O O C
Cu
C O
O C
O
O
2-
Figure 1.7 Structure of [Cu(C2O4)2] anion
presence of divalent metal ions like, Co2+, Ni2+, Zn2+, Cd2+, Cu2+, Hg2+ and Pb2+ and
3+ 3+ 3+ 3+ 3+
inner transition metal ions like, La , Pr , Nd , Sm and Gd are reported. An
attempt has also been made to use these complexes as precursors to prepare nano
metal oxides. Single crystals are prepared using 5-sulphosalicylic acid with hydrazine
and the structure has been found for the first time.
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.
33
SH-CHCOOH
SHCH2COOH CH2COOH COSH
HO
O
HO
S
OH
O O
Hydrazine complexes are found to yield metal oxides at low temperatures in the
nano scale, hence it was aimed to use the complexes to prepare nano metal oxides
using them as precursors
To study the isomorphism among the complexes using powder X-ray diffraction
technique
Based on the above objectives, this research work was performed and
the results obtained are discussed in the following chapters.