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toluidine systems are plotted in figs. 3.1 to 3.4. Phase- diagram study of
each system characterizes that there is the formation of two eutectics and
1:1 addition type compound with congruent melting point. Each phase
the melting point of the eutectic and the addition compound determined
from phase-diagram have been noted in Table 40. The colour, stoichiometry
agree well with the literature values. " The correctness and the
the synthesized one. Phase diagram study indicates that each system has a
equilibrium with liquid of same composition. From the first eutectic point
MOLE-FRACTION OF NAPHTHALENE
TEMPERATURE (°C)
Temperature
attains a maximum where the composition of liquid and solid phases are
identical, and this maximum temperature corresponds to the congruent
melting point of the addition compound. At the second eutectic point, the
eutectic mixture of the second component and the addition compound
separates out. A maximum point on liquids, flatness and length of the
middle branch of the curve and existence of eutectic point on either side of
the maximum provides information regarding the stability of the resulting
molecular compound. The addition compound is, of course stable in the
solid states and remains appreciably intact even in the molten state.3
2- Anthracene*-picric acid
(i) Eutectic-1 0.1017 109.5
(ii) Eutectic-2 0.6250 130.0
(iii)Addition compound 0.5 140.0
3- Phenanthrene*-picrid acid
(i) Eutectic-1 0.21 103.0
4- a-Naphthol*-p- toluidine
diagram has been shown in Fig. (1.2) and the boundary condition for the
components land 2 for the system under investigation are calculated from
melts deviate from unity, which confers a non-ideal character to the eutectic
mixtures.
peak at 395 nm and 360 nm and shoulders at 345 and 375 nm. While
96
eutectic-2 has a diffused broad band in the region. This may be due to
higher complex concentration in the second eutectic region than the first
eutectic and due to the blue shift on the high-energy side of the pure
a shoulder at 500 nm while eutectic-2 has the same at 510 nm. Anthracene-
picric acid complex has two shoulders at 510 nm and 450 nm. Also there is
the spectral features for example, the charge-transfer band and I.R. shifts are
state. In case of anthracene-picric acid complex, the I.R. shifts are of the
order of 5-10 cm'1 but using U.V. spectra makes an interesting observation.
grinding at 25:5, 50, 80, 120 and 155°C, it was observed that with the rise of
temperature, the colour of the sample changes from pink to dark red. The
U.V. spectra of these samples in nujol mull show a large red-shift of 410 nm
the perturbation of the bonds. From infrared spectra of eutectic and those of
interactions are operative during the formation of eutectics and they are not
3. Phenanthrene-picric acid
(i) Eutectic containing 0.21 mole
4. a-Naphthol- n- toluidine
and 25. From both the tables it has been noted that some reflections in the
have been found absent in the case of eutectics. The first eutectic formed
between picric acid and the charge -transfer complex has some reflections
with stronger intensifier having ‘d’ values 4.56, 4.18, 3.24 and 2.86 °A
reflections corresponding to ‘d’ values 5.39, 3.85, 2.85 and 2.67 °A have
stronger intensities. In both the case observed from tables 32 and 33, some
These experimental results infer, that these eutectics are not simply the
some atomic planes and a preferential ordering comes into existence during
with decreasing ‘d’ values. The eutectics are formed by the thermal
of the reflections can be accounted for by two facts. Firstly, there may be
may be due to thermal vibration of atoms forming the eutectics side of picric
under cooling for each system under investigation has been given in Fig. 3.5
materials. The values of k and n for pure components, eutectics and the
addition compound for each system have been given in Table 42 and in this
addition compound for each system, it can be inferred that excepting the
Ln At
>
►3
LOG V (mm/Sec)
i i
h3 J—* O
o o
rate slower than of picric acid but faster than that of phenanthrene. The
significantly slower than its parent compounds while in other case under
the melt have to enter the crystal lattice simultaneously in a way such that,
the composition of the melt conforms to 1:1 molar ratio of the two
crystallizing species.
2. Anthracene-nicric acid
The greater the slope the larger volume of n and the faster is to rate of
crystallization the first eutectic (mole fraction 0.2132) having a lower molar
acid is smaller than those of the parent components. The eutectic having
system with a difference that the eutectic with the lower (mole fraction 0.21)
its higher (mole fraction 0.815) value. The two eutectics formed in the case
than that having a lower (mole fraction 0.175) concentration of the same.
solidification begins with the formation of the nucleus of one of the phases.
This continues growing until the surrounding liquid becomes rich in the
other components starts nuclei. After that, two possibilities arise. In one, the
two initials crystals may grow side by side. This explains the cases in which
the rates of solidification of eutectics are not lower than those of the parent
107
complex have approximately the same degree of under cooling. For the
the nucleation of 1:1 complex. This continues, untill, the liquid become rich
in picric acid and a stage is reached when picric acid starts nucleating.
Similarly for the eutectic having higher mole fraction of naphthalene, due to
picric acid system, the eutectic with a lower mole fraction of anthracene
grow side by side and the velocity of eutectic lies between picric acid and
1:1 complex. On the other hand, the eutectic with a higher concentration of
complex. Due to a large gap between the "melting points of anthracene and
108
entropies of phases.5"8
from the value of their entropy of fusion. According to Hunt and Jackson
268, the type of growth from a eutectic melt depends upon a factor a, defined
as:
a =E, (3)
RT
the molecules and has the values less then, or, equal to one. Afh, R & T are
the heat of fusion, gas constant and the melting temperature. ASf/R is the
is the latent heat of the fusion, k is the Boltzman,s constant and Tm is the
A s:
(i) A s < 1, isotropic growth, cells and dendrites occur only with
impurity addition.
The above correlation retains the idea that a smaller the A s, smoother
Naphthalene 6.644 - - -
Anthracene : 7.070 - - -
Phenanthrene 6.017 - - -
a-Naphthol 7.696 - - -
p-Toluidine 6.898 - - -
eutectic-1
eutectic-2
5.655 _ _
Naphthalene-Picric acid
complex t
Anthracene-Picric acid 4.334 0.1800 Normal Complex
eutectic-1 Regular
eutectic-2
. .
Anthracene-Picric acid 7.259
complex
eutectic-1
eutectic-2
. .
Phenanthrene-Picric acid 5.376.
complex
eutectic-1
eutectic-2
_ .
a-Naphthol-p-toluidine 4.832
complex
3.5 Microstructure
kg. M" which is nearly twice that of the strongest known steel.
approximately parallel bands appear but the lamellar structure is not that
2. Microstriictures of eutectics.
equation9:
Ti-Te
0 =-------------- ..(4)
T2-Te
“between” 1.0 to 0.1 normal eutectics are found and for a range “between”
if the value of 0 lies below 0.01. The values of 0 for all eutectics of the
present systems have been given in the Table 44. A comparison shows that
structure has been observed. But the eutectic having lower mole fraction of
118
evident bands are observed and the view looks like a flower petal structure.
lamellar structure with uniqueness that there are fine parallel features
meeting at a point. On the other hand, the eutectic of the same with a lower
Compounds
toluidine was such that it has a tendency to break the lamellar growth. A
dendrite growth has also been observed due to impurity addition in case of
which a typical one is given in Fig. 3.19 the limit to which Hook’s law is
obeyed can be studied and the elastic-plastic character of the eutectics and
compounds in each system have been found greater than those of the pure
between the two-mole ties and large fracture value. These values along with
energy of the solid alloy due to moiety size disparity between -the two
UNDERCOOLING (4T )
ANTHRACENE
PICRIC ACID
ANTHRACENE-PICRIC
ACID EUTECTIC-1
ANTHRACENE-PICRIC
ACID EUTECTIC-2
ANTHRACENE-PICRIC
ACID COMPLEX
4 8 12 16 20 24
COOLING RATE (°C/MIN.)
Eutectic-1
Eutectic-2
Complex
Eutectic-1
Eutectic-2
Complex
Eutectic-1
Eutectic-2
Complex
122
Eutectic-2
Complex
Addition Compounds
has been compared with the experimental value. The observed and
COMPRESSION
and the heats fusion of components 1 and 2, are expressed by Afhi and Afh2.
association and heat of mixing causing violation of the mixture law. Besides
the heat of mixing, another factor, the interfacial tension, cjVs, may also
affect the magnitude of the heat of mixing. If found such, it may contribute
as:
where hE and A represent the excess heat of mixing and the surface area
respectively.
Rastogi et al.
KTe2
(Afh)e = -------------------------- (7)
[XeTBl + (l-Xe)TB2]
where Te,TBi and TB2 are the eutectic temperature, and the boiling
0.175 and Xe is the eutectic composition with respect to the first component.
calculated from equation (7), indicates that calculate value in each case is
higher than the experimental value. This difference in the two values of heat
melt. During cluster formation, there may be the liberation of heat, which
will consequently lower down the actual value of the heat of fusion. The
125
Naphthalene-Picric acid
Naphthalene-Picric acid
Eutectic-2 0.940 0.059 23.805 18.437 18.877
Naphthalene-Picric acid
Anthracene-Picric acid
Eutectic-1 0.101 0.858 41.348 19.584 20.473
Anthracene-Picric acid
Eutectic-2 0.625 0.375 38.640 24.018 25.217
Anthracene-Picric acid
Complex 0.5 0.5 31.726* 33.621 26.986
Phenanthrene-Picric acid
Eutectic-1 0.21 0.79 38.662 18.856 19.352
126
Phenanthrene-Picric acid
Eutectic-2 0.815 0.185 28.576 18.083 18.777
Phenanthrene-Picric acid
Complex 0.5 0.5 24.526* 31.039 22.018
a-Naphthol-p-toluidine
a-Naphthol-p-toluidine
a-Naphthol-p-toluidine
Afh 1 1
= -ln(xA)m (xBf + ln(xA)c m(xB)cn ..(8)
R T Tc
addition compound with the molecular formula AmBn.Afh and R are heat of
127
case it is observed that the two values agree well within the experimental
limits.
eutectics
and ordering in the eutectic melts. The entropy of fusion and excess
Afh
As = ------
T
Where Afh is the heat of fusion and T is the fusion temperature. The
increase in the randomness of the system during melting. The eutectics have
the observed value of entropy of fusion for the present systems it can be
to the calculated value suggests that the system may exist in a slightly
disordered state, which can very easily be inferred from its appreciably
mixing, s for the eutectics have been calculated by the following procedure
ITSInyi T 81ny2
se = -R xilnyi + x2lny2 +xi ----------- +x2----------- (10)
8T 8T
Slnyi Slny2
hE = -RT2 xi + x2------- (11)
8T 8T
given by:
Afhi0
-Inx,7i= ------ (T'-Tf1) (12)
R
Where Xi, Vi, Afhi, Ti° are the mole fraction, activity coefficient, heat
8Invi/ST have been determined from the phase-diagram through the slope of
As below:
X! 8T 8T RT2
the region of eutectic composition. The value of Xj/ T can be calculated as:
Xi = a + (3T (14)
The table for excess thermodynamic functions indicate that the value
of the excess free energy confirms the interaction between the two
association of the weaker nature. The sign of excess free energy may
eutectics.
Anthracene-Picric acid
Eutectic-2 0.095 -0.783 0.001 0.805
Phenanthrene-Picric acid
Eutectic-1 0.102 -1.325 0.012 0.345
Phenanthrene-Picric acid
Eutectic-2 0.080 0.215 0.030 0.759
a-Naphthol-p-toluidine
eutectic-1 0.029 0.218 0.040 1.563
a-Naphthol-p-toluidine
eutectic-2 0.033 0.975 0.205 0.057
Naphthalene 0.053 - - -
Anthracene 0.058 - - -
Phenanthrene 0.498 - -
a-Naphthol 0.636 - - -
p-Toluidine 0.570 - - -
131
very easily calculated by the following equation and thereby an insight into
obtained:
respectively for the component i. The heats of mixing of eutectics and that
of addition compound for each system under investigation have been given
in Table 47. The sign and the magnitude of the heat of mixing of a system
governs its type of structure present therein. Strong interactions between
unlike molecules are expected when the heat of mixing is negative, while
for a positive heat of mixing quasi-eutectic structures are suggested. From
the Table 47 it is clear that the addition compound in each case has a very
heats of mixing for the eutectics show the tendency of ordering in the melts.
Situations for the eutectics are a bit more complicated because each eutectic
may be supposed to be formed of the addition compound and one of the
131
very easily calculated by the following equation and thereby an insight into
obtained :
respectively for the component i. The heats of mixing of eutectics and that
of addition compound for each system under investigation have been given
in Table 47. The sign and the magnitude of the heat of mixing of a system
governs its type of structure present therein. Strong interactions between
unlike molecules are expected when the heat of mixing is negative, while
the Table 47 it is clear that the addition compound in each case has a very
heats of mixing for the eutectics show the tendency of ordering in the melts.
Situations for the eutectics are a bit more complicated because each eutectic
parent components. The heats of mixing of all the eutectics of these systems
are negative. The values of heat of mixing for eutectics are very low in
comparison to the values of the same , for the corresponding addition
These results are quite different from those observed in case of simple
eutectic systems where merely ordering of the parent phases comes into
existence in the eutectic melt. In addition, it appears that there is a
Compund
Naphthalene-Picric
Anthracene-Picric
Phenanthrene-Picric
from the arrest or several point on the continuous cooling curves, the effect
of variants such as the cooling rate, freezing cycle number, quantity of melt,
and the alloy composition have not been adequately accounted for or have
been totally ignored. For an arrest or reversal of cooling curve to occur, the
significantly higher cooling rates than the lower melting ones. The results
derived from the Fig 3.21 to 3.27.
134
UNDERCOOLING (AT)
00 to
to o\ o
P
31 VU ONHOOG
8
(NIIAI/Oo)
Zl
A------- A
▲----A
□ ----- □
o
COMPLEX
EUTECTIC-2
NAPHTHALENE
EUTECTIC-1
PICRIC ACID
OO
VO
*
—H
UNDERCOOLING (A.T)
to
NAPHTHALENE
OO
PICRIC ACID
NAPHTHALENE PICRIC
ACID EUTECTIC-1
NAPHTHALENE PICRIC
Ov
ACID EUTECTIC-2
NAPHTHALENE PICRIC
ACID COMPLEX
"0 1 2 3 4 5 6 7 8 9
FREEZING CYCLE NUMBER
* 9 t
UNDERCOOLING (AT)
UNDERCOOLING (AT)
ANTHRACENE
PICRIC ACID
PHENANTHRENE-PICRIC
ACID EUTECTIC-1
PHENANTHRENE-PICRIC
ACID EUTECTIC-2
PHENANTHRENE-PICRIC
ACID COMPLEX
4 8 12 16 20 24
COOLING RATE (°C/MIN.)
A-----A---- A-
UNDERCOOLING (AT)
ANTHRACENE
PICRIC ACID
PHENANTHRENE-PICRIC
ACID EUTECTIC-1
PHENANTHRENE-PICRIC
ACID EUTECTIC-2
PHENANTHRENE-PICRIC
ACID COMPLEX
18 O____ q a-naphthol
___ /\ p-toluidine
12
UNDERCOOLING (A.T)
o
oo
o0 0
'O
oS3
0 1 23 45 67 8 9 10
The observations made on these systems indicate that in each case the
simplest case, assuming spherical growth and a constant radial growth rate,
by the cooling rate. If the nucleation rate is not sufficiently increased with
increased cooling rate, then liquid/solid mixture will super cool to a lower
depends upon the number of freezing cycles used. The effect of freezing
demonstrated in Figs. From 3.26 to 3.27 The results indicate that initially
142
the melt nucleated only after few degrees below the equilibrium liquids
depending upon the nature of the melt. The saturation cycle number for the
pure components was found to be smaller than those for the eutectics and
the complex. This can be explained such that the nucleants are responsible
achieved when all the nucleants are removed in this way. The removal of
The results from the observations made on the effect of the quantity of the
observed to vary with the total quantity of the sample. It has been observed
that in each case the degree of undercooling decreases with the increase of
the quantity of the melt. For various systems the trend of the effect is almost
281
Flemings this can be explained by arguing that a simple thermal balance
between the rate of evolution of latent heat of fusion and rate of loss of heat
point. When the melt is in small quantity, the available latent heat may not
temperature for a bulk sample, as determined from the cooling curve, can
cycle number and the alloy composition. The effect of these parameters on
REFERENCES
1. R.Foster, 'Organic charge transfer complexes 'Academic Press,
(1988) 265.
3. N.B. Singh, B.M.S., Mol Cryst Liqu. Cryst. 104 (1984) 265.
5. J.D. Hunt and K.A. Jackson, Trans AIME 236 (1966) 843.
7. W. Kurtz and D.T. Fischer, Inten Metals Rev. 5/6 (1979) 177.
8. V.V. Podolinsky and V.G. Drykin Zh. Fiz. Khim 61 (1987) 499.
12. U.S. Rai, D.P.S. Singh N.B., Thermo Chimica Acta 71 (1983) 373.
14. G.L.F. Powell and G.A. Colligen Trans Met. Soc. ACME (1969) 245,
1913.
16. G.T. S loan and A.R. Maghir J. Cryst growth 32, 60 (1976).