CHAPTER-3

RESULTS AND DISCUSSION

In this present chapter the results derived on the basis of the

experimental findings given in the chapter II, for naphthalene-picric acid,

anthracene- picric acid, phenanthrene-picric acid and oc-naphthol-p-

toluidine systems have been discussed, under the following heads:

3.1 Phase- Diagram

The solid- liquid equilibrium data for naphthalene- picric acid,

anthracene- picric acid, phenanthrene-picric acid and a-naphthol-p-

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

diagram may be supposed to consist of two phase- diagrams in which the

addition compound serves as one of the components. The composition and

the melting point of the eutectic and the addition compound determined

from phase-diagram have been noted in Table 40. The colour, stoichiometry

and the melting point of addition compounds derived from phase-diagram

agree well with the literature values. " The correctness and the

dependability of the phase- diagram has been checked by comparing it with

the synthesized one. Phase diagram study indicates that each system has a

(1:1)' molecular compound capable of existing as a solid compound in

equilibrium with liquid of same composition. From the first eutectic point

onwards, on addition of the second component, the melting point rises,

 90
TEMPERATURE (°C)

MOLE-FRACTION OF NAPHTHALENE

Fig.3T: Phase-diagram of naphthalene-picric acid system

 91
TEMPERATURE (°C)

FIG3.2: Phase-diagram of anthracene-picric acid system

 92

TEMPERATURE (°C)

FIG3.3: Phase-diagram of Phenanthrene-picric acid system

 93

Temperature

FIG.3.4: Phase-diagram of a-naphthol-p-toluidine System

 94

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

Table 40: composition and melting point of eutectics and

compound of various system.
System Composition Melting
(mole fraction of point
first*componenf) (°C)
l-Naphthalene*-picric acid
(i) Eutectic-1 0.2132 107.5

(ii) Eutectic-2 0.9405 73.5

(ii) Addition compound 0.5 155.0

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

(ii) Eutectic-2 0.815 85.0

 95

(iii) Addition compound 0.5 145.0

4- a-Naphthol*-p- toluidine

(i)Eutectic-l 0.175 31.0

(ii) Eutectic-2 0.595 51.5

(iii) Addition compound 0.5 58.5

For a system having a congruent melting point, a typical phase

diagram has been shown in Fig. (1.2) and the boundary condition for the

coexistence curves AE and BE may be givens by the eqn.l. Provided the

mixture behaves ideally, the eutectic composition and temperature can be

predicted by solving eqns. (in chapter I). The activity coefficients of

components land 2 for the system under investigation are calculated from

the following equation and are given in Table 41.

= -In x1, yi1 = Aft0 / R (T/1 - Tf1) ...........(1)

The activity coefficient of the components constituting the eutectic

melts deviate from unity, which confers a non-ideal character to the eutectic

mixtures.

3.2 Spectral Studies

The spectral studies confirm the increased interactions between the

two components leading to the complex formation in each system. Eutectic-

I of naphthalene- picric acid has no peak around 650 nm while eutectic-2

has a distinct band at 650nm. In 400-300 nm ranges, eutectic-I has a distinct

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

component band. Similarly, for anthracene-picric acid system, eutectic-1 has

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

significant intensity variation on the low energy peaks of the pure

components between 400-300 nm region. This is due to substantial effects

of complexation on these transitions. In case of charge -transfer complexes,

the spectral features for example, the charge-transfer band and I.R. shifts are

similar to liquid solution spectra with a slight modification due to solid

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.

While preparing the homogeneous composition by heating, chilling and

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

shoulder at 25.5°C to 468 nm at 155°C. However, the shoulder at 510 nm

remains unchanged. This may be due to an increased interaction leading to

the perturbation of the bonds. From infrared spectra of eutectic and those of

the parent components it may be concluded that some appreciable

interactions are operative during the formation of eutectics and they are not

simply the mechanical mixture of the two components.

 97

Table 41- Activity coefficients for eutectic systems

. System In yi Iny2

1, Naphthalene-picric acid system

(i) Eutectic containing 0.2132

mole fraction of naphthalene 2.014 0.024

(ii) Eutectic containing 0.9405

mole fraction of naphthalene 0.05 2.004

2. Anthracene-picric acid system

(i) . Eutectic containing 0.1017

mole fraction of anthracene 0.322 -0.073

(ii) Eutectic containing 0.6250

mole fraction of anthracene -1.046 1.107

3. Phenanthrene-picric acid
(i) Eutectic containing 0.21 mole

Fraction of phenanthrene 1.596 -0.064

(ii) . Eutectic containing 0.815 mole

fraction of phenanthrene -0.100 1.031

4. a-Naphthol- n- toluidine

(i) Eutectic containing 0.175 mole

Fraction of a-naphthol 2.16 0.015

(ii) Eutectic containing 0.595 mole

fraction of a-jnaphthol 0.543 1.875

 98

X- ray diffraction studies of some system have been made and as a

representative, data for anthracene-picric acid system are given in Tables 24

and 25. From both the tables it has been noted that some reflections in the

eutectics have relatively stronger intensities as compared to the similar lines

in pure components and charge-transfer complex. More over, some lines

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

whereas some reflections of picric acid and charge-transfer complex are

missing. In case of the second eutectic formed between anthracene and

charge- transfer complex a similar trend is observed. In this eutectic the

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

reflections of the eutectics show the deviations in inter planar distances.

These experimental results infer, that these eutectics are not simply the

mechanical mixtures of the two components. In them, there is orientation of

some atomic planes and a preferential ordering comes into existence during

the formation of such eutectics.

The intensities of the reflections, as is clear from the tables diminish

with decreasing ‘d’ values. The eutectics are formed by the thermal

activation of interaction of the parent components, and decrease in intensity

of the reflections can be accounted for by two facts. Firstly, there may be

some disorder of location of atoms forming the eutectics and secondly, it

may be due to thermal vibration of atoms forming the eutectics side of picric

acid and the second eutectic at a higher concentration side of anthracene

 99

whereas, the complex is formed at the equimolar concentration. From the

X- ray powder photographs of the pure components, eutectics and the

complex , it can be observed that there is a marked difference in inter planar

spacing and relative intensity of these compounds. Moreover, the x-ray

patterns indicate that the eutectics are crystalline in character.

3.3 Linear Velocity of crystallization

The linear velocity of crystallization (movement of solid -liquid

interface) of pure components, eutectics and addition compound at various

under cooling for each system under investigation has been given in Fig. 3.5

to 3.8 and follows the Hilling- Turnbull equation 4:

V = k(AT)n ----------- (2)

Where v is the linear velocity of crystallization, AT is the under

cooling k and n are constants depending on the solidification behaviour of

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

context the eutectics and addition compound may be discussed separately.

The deviation of the numerical value of n from 2 may be attributed to the

diff. In temperature of the interface and the bath.

1. Parent components and 1:1 addition eomnound-

On comparing the values of k for the pure components and the

addition compound for each system, it can be inferred that excepting the

addition compound of phenanthrene with picric acid, the naphthalene-picric

acid, anthracene- picric acid and a-naphthol-p-toluidine addition

compounds crystallize slowly as compared to their parent components. The

addition compound of phenanthrene with picric acid crystallizes with

 100

FIG. 3.5: Linear Velocity of crystallization at various degree of

undercoolings for naphthalene-picric acid System.
 101

Ln At
>

►3

FIG. 3.6: Linear Velocity of crystallization at various degree of

undercoolings for Anthracene-picric acid System.
 102

FIG. 3.7: Linear Velocity of crystallization at various degree of

undercoolings for Phenanthrene-picric acid System,.
 103

LOG V (mm/Sec)
i i
h3 J—* O
o o

FIG. 3.8: Linear Velocity of crystallization of oc-naphthol-p-

Toludine at Various under cooling.
 104

rate slower than of picric acid but faster than that of phenanthrene. The

crystallization rate of the naphthalene-picric acid addition compound is

significantly slower than its parent compounds while in other case under

investigation the crystallization rate of the addition compound lies in the

vicinity of either if the components. Studies on crystal morphology of

addition compound indicate that they should crystallize as a definite

chemical entity. However, during crystallization the two components from

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

components. Due to this, the linear velocity of crystallization of the addition

compounds may be expected to be of the order of the velocity of the slowly

crystallizing species.

Table 42: Values of k and n for pure components, eutectics and

addition compound for each system.
System k n

Nm. Sec'1 deg'1

1. Nanhthalene-Dicric acid svstem

(0 Naphthalene 1.514 1.88

(ii) Picric acid 0.273 1.56

(hi) Eutectic-1 0.005 1.37

(iv) Eutectic-2 0.00005 2.42

(v) (1:1) addition compound 0.00002 3.75

2. Anthracene-nicric acid

(0 Anthracene 0.235 1.39

 105

(ii) Eutectic-1 0.058 2.15

(iii) Eutectic-2 0.039 1.71

(iv) (1:1) addition compound 0.064 1.55

3.Phenanthrene-t)icric acid system

(i) Phenanthrene 5.6234x10'6 0.40
(u) Eutectic-1 i 1.1482x1 O'6 0.67

(iii) Eutectic-2 1.9953xl0'6 1.00

(iv) (1:1) addition compound 7.2444x1 O'6 0.81

4. a-Naohthol - n- toluidine system

(i) a-Naphthol 1.49x1 O'4 3.48

(ii) p-Toluidine 3.08x1 O'4 3.62

(iii) Eutectic-1 4.47x1 O'4 2.35

(iv) Eutectic-2 3.03x10'4 2.29

(1:1) addition compounds 1.09x1 O’4 3.30

(ii) Parent components and eutectics- the linear velocity of crystallization

of eutectics varies with the degree of under cooling according to Hilling-

Tumbull equation (2).

Comparing the magnitudes of k from Table 42 has derived the mode

of crystallization of eutectics. In naphthalene picric acid system both

eutectics have solidification rates lying between those of the' parent

components. Although, the plot of log v verses log AT obtained in cases of

parent components are true indicators to assess the rate of crystallization.

 106

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

concentration of naphthalene solidifies faster than the second eutectic of

mole fraction 0.9405) i.e., with a higher molar concentration of naphthalene.

The solidification rate of the two eutectics of anthracene in picric in picric

acid is smaller than those of the parent components. The eutectic having

higher concentrations of anthracene (mole fraction 0.6250) solidifies slowly

as compared to that having its lower concentration mole fraction 0.1017).

Similar observation has been made in case of phenanthrene- picric acid

system with a difference that the eutectic with the lower (mole fraction 0.21)

concentration of phenanthrene solidifies slowly as compared to that having

its higher (mole fraction 0.815) value. The two eutectics formed in the case

of c- naphthol-p- toluidine system have solidification rates higher than those

of the parent components. The eutectic having a higher (mole fraction

0.595) concentration of a-naphthol undergoes solidification with rate faster

than that having a lower (mole fraction 0.175) concentration of the same.

These solidification phenomena may be explained in the light of the

mechanism proposed by Winegard et al. According to this, the eutectic

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

components. In another possibility, there may be alternate. This explains the

solidification phenomena in cases where the linear velocity of crystallization

of the eutectics is lower than that of the parent components. The

solidification of both the eutectics of naphthalene-picric acid, anthracene-of

both the eutectics of naphthalene-picric acid, anthracene-picric acid and

phenanthrene-picric acid may take place by alternate nucleation of two

components while the solidification of the a-naphthol- p-toluidine eutectics,

may be due to side by side growth of the two components.

In naphthalene-picric acid system, parent components, eutectics and

complex have approximately the same degree of under cooling. For the

eutectic with a lower mole fraction of naphthalene, crystallization starts with

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

lower melting temperature of naphthalene there is possibility of nucleation

of 1:1 complex first, followed by nucleation of naphthalene. In anthracene-

picric acid system, the eutectic with a lower mole fraction of anthracene

follows the same course of crystallization. When the eutectic melt

undercools (1:1) complexes usually nucleates on picric acid. The phases

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

anthracene crystallizes with the nucleation of anthracene followed by 1:1

complex. Due to a large gap between the "melting points of anthracene and
 108

(1:1) complex there is a very low possibility of alternate nucleation. The

lower crystallization velocity of this eutectic as compared to that of

anthracene and 1:1 complex can thus be explained.

3.4 Interface Roughness

The structure of eutectic alloys presents great interest for practical

applications. Important classification of eutectic is based on melting

entropies of phases.5"8

The growth morphology depends developed by a eutectic system

during solidification depends upon the growth characteristics of the

individual constituent phases, on the basis of which phases solidity with

either faceted or non-faceted interfaces. This phenomenon of solidification

is related to the nature of the solid-liquid interface and can be predicted

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

Where £ is crystallographic factor depending upon the geometry of

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

entropy of fusion in dimensionless unit. When a < 2, non-faceted growth

occurs whereas a faceted growth appears, if a > 2.

 109

The shape of growth surfaces in macroscopic crystals may be

correlated with their entropy of fusion given 269 as A s = Lf/kTm, where Lf

is the latent heat of the fusion, k is the Boltzman,s constant and Tm is the

melting point. Four classes of materials can be distinguished on the basis of

A s:

(i) A s < 1, isotropic growth, cells and dendrites occur only with

impurity addition.

(«) 2 < A s ^ 4, faceted growth, faceted “pseudodendrites” with

sufficient impurity addition.

(iii) A s ^ 4, facets always observed.

(iv) A s it 10, spherulitic growth usual.

The above correlation retains the idea that a smaller the A s, smoother

a growth surfaces will be. High As suggests high randomness or roughness

in growth surfaces with a resultant tendency to ward dendrites, facet effects,

and spherulitic growth. Spherulitic growth or growth of many crystals

radially outward from a point is most commonly observed in polymers,

facet growth in semi-conductors, dendrites in metals and isotropic growth in

inorganic and short chain organic materials. The values of Jackson

roughness parameter (c) given in table 43 indicates that for pure

components, eutectics and addition compound, a is greater than 2.

Therefore, this investigation predicts that the solid-liquid interfaces may be

automatically smooth, advance in atomic steps and exhibit a tendency to

develop a faceted morphology, which may be correlated with the micro

structural investigations done on these systems.

 110

Table 43: Jackson’s roughness parameter (a) and Spengler’s

parameter (a) for various systems.
System J.R.P. cj ] dicrostrueture

(a) Computed Observed

Naphthalene 6.644 - - -

Anthracene : 7.070 - - -

Phenanthrene 6.017 - - -

a-Naphthol 7.696 - - -

Picric acid 5.980 - - -

p-Toluidine 6.898 - - -

Naphthalene-Picric acid 5.961 0.1772 Normal Lamellar

eutectic-1

Naphthalene-Picric acid 6.418 0.1376 Normal Lamellar

eutectic-2

5.655 _ _
Naphthalene-Picric acid

complex t
Anthracene-Picric acid 4.334 0.1800 Normal Complex

eutectic-1 Regular

Anthracene-Picric acid 6.178 0.0913 Anomalous Lamellar

eutectic-2
. .
Anthracene-Picric acid 7.259

complex

Phenanthrene-Picric acid 6.061 0.0168 Anomalous Lamellar

eutectic-1

Phenanthrene-Picric acid 6.145 0.0399 Anomalous Irregular

 Ill

eutectic-2
. .
Phenanthrene-Picric acid 5.376.

complex

a-Naphthol-p-toluidine 3.025 0.0217 Anomalous Irregular

eutectic-1

a-Naphthol-p-toluidine 5.100 0.0144 Anomalous Irregular

eutectic-2
_ .
a-Naphthol-p-toluidine 4.832

complex

3.5 Microstructure

The microstructure of a material has been found significantly

important in deciding its mechanical, electrical, magnetic and optical

properties. Certain ferromagnetic materials show 4 to 5 fold improvement in

magnetic properties when present in needle-like crystals. Directionally

3
solidified Cr-Cu eutectic fibers show tensile strengths of over 7030.7 x 10

kg. M" which is nearly twice that of the strongest known steel.

1. Microstructures of pure components and 1:1 addition compound

On analysing the microstructures (Fig. 3.9 to 3.18) of the pure

components and the addition compound of various systems under

investigation it is observed that in case of (1:1) addition compound of

anthracene-picric acid a coarse fibrous structure having Chinese script in

certain regions is obtained. In addition compound of phenanthrene with

picric acid a quashregular structure extending from various nucleatior

centers has been observed. Similar irregular structure in a-naphthol-p-

 112

Fig. 3.9: Modular structure of Eutectics

Fig. 3.10: Rod like structure of Eutectic-1 :Complex

 113

Fig. 3.11: Rod type structure

Fig. 3.12: Dendritic structure of Eutectic faceted

 114

Fig. 3.13: Micro structure of 1: complex

anthracene-picric acid.

Fig. 3.14: Micro structure of Eutectic a -

nephthol-p-toluidine
 115

Fig. 3.15: Micro structure of 1: Complex a -

nephthol-p-toluidine

Fig. 3.16: Micro structure of Eutectic

Phenanthrene-picric acid.
 116

Fig. 3.17: Micro structure of 1: Complex

Phenathrene-picric acid.

Fig. 3.18: Micro structure of Eutectic Naph­

thalene-picric acid.
 117

toluidine (1:1) addition compound has been obtained while in case of

naphthalene-picric acid addition compound although in certain regions

approximately parallel bands appear but the lamellar structure is not that

convince in due to irregular growth and shrinking of the lamellae. Those

observations conclude that the microstructures are irregular and complex,

which indicates that addition compound, and the parent components

undergo crystallization in the same fashion and the addition compounds

behave like a single compound

2. Microstriictures of eutectics.

A prediction of microstructure of eutectics can be made from Spenglers

equation9:

Ti-Te
0 =-------------- ..(4)
T2-Te

Where Ti,T2 and Te are melting temperature of low melting high

melting components and eutectic respectively. For value of 0 lying

“between” 1.0 to 0.1 normal eutectics are found and for a range “between”

0.1 to 0.01 anomalous structures are obtained. A diversed structure appears

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

in most of the cases, the microstructures predicted on the basis of Spangler’s

equation, fit well with the microstructure observed.

In case of both the eutectics of naphthalene-picric acid a lamellar

structure has been observed. But the eutectic having lower mole fraction of
 118

naphthalene shows a close lamellae while that consisting of a higher mole

fraction of the same exhibit lamellae of wider width. In case of anthracene-

picric acid eutectic containing 0.1017mole fraction of anthracene quite

evident bands are observed and the view looks like a flower petal structure.

The eutectic of the same with 0.6250mole fraction of anthracene has a

lamellar structure with uniqueness that there are fine parallel features

extending in different orientations. In case of phenanthrene-picric acid

eutectic having 0.815mole fraction of phenanthrene, lamellar structure has

been obtained. Lamellae appear to be either extending in two directions or

meeting at a point. On the other hand, the eutectic of the same with a lower

mole fraction of phenanthrene exhibits an anomalous feather like structure.

In case of a-naphthol-p-toluidine eutectic the microstructures observed have

been found of anomalous type.

3.6 Morphology Modification of Eutectic and 1:1 Addition

Compounds

Moreover, the effect of addition of anthracene on the microstructure

of the addition compounds of naphthalene-picric acid, phenanthrene-picric

acid a-naphthol-p-toluidine was significant in the sense that it has a marked

tendency in making fibrous structure. Due to impurity addition, a star like

structure with obvious nucleation centers extending in all directions has

been observed. On adding naphthalene as impurity to the. addition

compound of anthracene-picric acid, a feather like structure appeared.

 119

Similarly the effect of addition of anthracene to the eutectics of

naphthalene- picric acid, phenanthrene-picric acid and a-naphthol-p-

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

a-naphthol-p-toluidine eutectic with the lower concentration of a-naphthol.

3.7 Mechanical Properties

The mechanical properties of parent components, eutectics and

addition compounds studied by Instron technique have been found

significantly important. From the load-compression curve of the samples for

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

addition compound can be derived. Data for mechanical properties studied

are given in Table 45.

The fracture value and the modules of elasticity of the addition

compounds in each system have been found greater than those of the pure

components. This enormous increase in the fracture value of the addition

compound over those of the pure components may be attributed to the

established additional binding forces due to the molecular interactions

between the two-mole ties and large fracture value. These values along with

the compressibility of the alloyes play an important role in evaluation strain

energy of the solid alloy due to moiety size disparity between -the two

components as suggested by several workers.10,11

 120

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.)

FIG. 3.19: Effect of cooling rate on degree of undercooling of

anthracene-picric acid system.
 121

Table 44: Fracture value and Module of elasticity of parent components

and complex.
System Fracture value Modulus of
Kg. M2 elasticity
Naphthalene 61.211x103 1.984

Picric Acid 26.027x103 . 1.783

Naphthalene-Picric acid 46.713xl03 2.062

Eutectic-1

Naphthalene-Picric acid 39.853xl03 1.995

Eutectic-2

Naphthalene-Picric acid 255.061xl03 27.040

Complex

Anthracene 83.04x103 3.098

Anthracene-Picric acid 68.952xl03 2.153

Eutectic-1

Anthracene-Picric acid 80.417xl03 2.897

Eutectic-2

Anthracene-Picric acid 217.561xl03 21.050

Complex

Phenanthrene-Picric acid 62.839xl03 2.001

Eutectic-1

Phenanthrene-Picric acid 49.086x103 2.364

Eutectic-2

Phenanthrene-Picric acid 86.752xl03 3.789

Complex
 122

a-Naphthol 78.893xl03 2.895

p-Toluidine 38.093x103 1.952

a-Naphthol-p-toluidine 19.836x103 1.000

Eutectic-1

a-Naphthol-p-toluidine 47.683x103 2.095

Eutectic-2

Oc-Naphthol-p-toluidine 69.384x103 2.876

Complex

3.8 Thermo chemistry and Thermodynamics of Eutectics and

Addition Compounds

In order to understand the nature of crystallization of eutectics and the

addition compound, their heat of fusion has been determined

experimentally. The theoretical value of heat of fusion of eutectics and that

of addition compound computed on the basis of thermodynamic equations

has been compared with the experimental value. The observed and

calculated values heat of fusion of eutectics and those of addition compound

are given in Table 46.

3.9 Heat of Fusion of Eutectics

Supposing the eutectics to be a simple mixture of the two components

involving no heat of mixing or any type association in the melt, heat of

fusion may be given by the mixture law :

(Afh)e = XiAfhj + x2Afh2 ..(5)

 123

COMPRESSION

FIG 3.20: LOAD-COMPRESSION CURVE OF ANTHRACENE-

PICRIC ACID COMPLEX.
 124

Where Xi and X2 are the mole fractions of component 1 and 2 respectively,

and the heats fusion of components 1 and 2, are expressed by Afhi and Afh2.

But when a solid eutectic melts, there is a considerable possibility of

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:

(Afh)e = Xi Afhi + x2Ath2 + hE + <A-s (6)

where hE and A represent the excess heat of mixing and the surface area

respectively.

In order to compute the heat of fusion of various organic eutectics, an

empirical equation, based on several possible factors, has been proposed by

Rastogi et al.

KTe2
(Afh)e = -------------------------- (7)
[XeTBl + (l-Xe)TB2]
where Te,TBi and TB2 are the eutectic temperature, and the boiling

points of the components 1 and 2 respectively. K is a constant; equal to

0.175 and Xe is the eutectic composition with respect to the first component.

The comparison of the observed value of heat of fusion with that

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

of fusion of eutectic may be due to the formation of clusters in the eutectic

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

cluster formation will be favoured due to the molecular association by

certain weak intermolecular forces. The cluster formation will be more
enhanced if certain groups helping in the formation of hydrogen bond, are
present in one or both the components of the eutectic system.
Table 45: Observed and calculated Values of heat of fusion of eutectics

and addition compounds.

Heat of fusion (kj/MK) Calculated from Observed

System 1-Xe

Eqn. 3/4* eqn.l

Naphthalene-Picric acid

Eutectic-1 0.213 0.786 39.516 18.789 19.398

Naphthalene-Picric acid
Eutectic-2 0.940 0.059 23.805 18.437 18.877

Naphthalene-Picric acid

Complex 0.5 0.5 21.875* 24.210 20.018

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

Eutectic-1 0.175 0.825 29.321 .18.929 18.845

a-Naphthol-p-toluidine

Eutectic-2 0.595 0.405 35.732 19.968 19.216

a-Naphthol-p-toluidine

Complex 0.5 0.5 23.126* 24.318 21.432

3.10 Heat of fusion of addition compound

The phase boundary and heat of fusion of the congraently melting

(1:1) addition compounds have theoretically been calculated with the help
of the following equation :

Afh 1 1
= -ln(xA)m (xBf + ln(xA)c m(xB)cn ..(8)
R T Tc

Where xA and xB are the mole fractions of the components A, B and

Tc denotes the congruent melting temperature and the quantities with the
subscript c denote the mole fraction corresponding to that of the molten

addition compound with the molecular formula AmBn.Afh and R are heat of
 127

fusion and gas constant respectively. On comparing the computed values of

heat of fusion of addition compound with the experimental values in each

case it is observed that the two values agree well within the experimental

limits.

3.11 Entropy of fusion and excess thermodynamic functions of

eutectics

The theoretical studies on entropy of fusion and calculations of some

excess thermodynamic functions of eutectics predict the structure stability

and ordering in the eutectic melts. The entropy of fusion and excess

thermodynamic functions of eutectics are given in Table 47.

The entropy of fusion As has been calculated from the relation:

Afh
As = ------
T
Where Afh is the heat of fusion and T is the fusion temperature. The

entropy of fusion in each system under investigation being positive infers an

increase in the randomness of the system during melting. The eutectics have

a lower entropy of fusion as compared to the pure components. In view of

the observed value of entropy of fusion for the present systems it can be

concluded that these eutectic systems go insubordination with the Richard’s

rule. Moreover, the lower observed value of entropy of fusion as compared

to the calculated value suggests that the system may exist in a slightly

disordered state, which can very easily be inferred from its appreciably

homogeneity range of composition.

In order to know the nature of interaction between the components

forming the eutectics, some thermodynamic functions such as the excess

 128

free energy, gE , excess enthalpy of mixing, hE and excess entropy of

mixing, s for the eutectics have been calculated by the following procedure

The eutectic temperature and composition can be determined from the

phase-diagram of the system. The excess thermodynamic function have

been calculated from the following equations (9,10&11) given below:

gE = RT (xi 1 ny i + x21 ny2) (9)

ITSInyi T 81ny2
se = -R xilnyi + x2lny2 +xi ----------- +x2----------- (10)
8T 8T

Slnyi Slny2
hE = -RT2 xi + x2------- (11)
8T 8T

The activity coefficient of a component I present in a system can be

given by:
Afhi0
-Inx,7i= ------ (T'-Tf1) (12)
R

Where Xi, Vi, Afhi, Ti° are the mole fraction, activity coefficient, heat

of fusion and the melting temperature of the component i. R is the gas

constant and T the melting temperature of the system. The values of

8Invi/ST have been determined from the phase-diagram through the slope of

the liquids curve using equation (12)

As below:

On differentiating equation (12) we get.

 129

-1 5xi Slnyi AJhi0

X! 8T 8T RT2

Xi 8 lnyi xi Afhi° Sxi

or (13)
8T RT2 8T

The liquidus curves in phase -diagrams are virtually straight line in

the region of eutectic composition. The value of Xj/ T can be calculated as:

Xi = a + (3T (14)

where a and p are constants and p = 8xi /ST

The table for excess thermodynamic functions indicate that the value

of the excess free energy confirms the interaction between the two

components of eutectics. A negative value of excess free energy leads to a

strong association while a positive value of the same indicates an

association of the weaker nature. The sign of excess free energy may

provide an information regarding the increase or decrease of density during

the phase-transformation. The excess entropy is a measurement of change in

configurational energy due to change in potential energy and it indicates an

increase in randomness. The excess enthalpy of eutectic in each case under

study has been found positive. These

 130

Table 46: Entropy of fusion and excess thermodynamic functions of

eutectics.

System Entropy of Excess Excess Excess

Fusion free entropy
enthalpy energy sE hE
gE
KJM^K'1 KJM^K'1 KJM^K'1 KJM^K1
Naphthalene-Picric acid
Eutectic-1 0.050 1.622 0.005 3.602
Naphthalene-Picric acid
Eutectic-2 0.054 0.563 0.023 0.025
Anthracene-Picric acid
Eutectic-1 0.107 -0.185 0.183 2.986

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 - -

Picric acid 0.495 - -

a-Naphthol 0.636 - - -

p-Toluidine 0.570 - - -
 131

thermodynamic calculations lead to the conclusion that there will be an

appreciable interaction between the two components of the eutectics.

3.12 Heat of mixing of eutectics and addition compound

The best of mixing of an eutectic or an addition compound can be

very easily calculated by the following equation and thereby an insight into

the structure of melts in -binary eutectics and addition compounds may be

obtained:

(Af h)M = (Af h)exp. - Xi Af hi0 ..(15)

Where fhexp is the heat of fusion of the system determined

experimentally, xi and Af hi° are the mole fraction and heat of fusion,

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

high exothermic heat of mixing. Anthracene-anthracene, phenanthrene-

phenanthrene, naphthalene-naphthalene, picric acid-picric acid, a-naphthol -

a-naphthol and p-toluidine - p-toluidine interactions are very weak as

compared to the arene-picric acid or a-naphthol - p-toluidine interactions.

The exothermic mixing confirms the compound formation in each case,

which is in accordance with the phase-diagram and spectral studies. The

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

thermodynamic calculations lead to the conclusion that there will be an

appreciable interaction between the two components of the eutectics.

3.12 Heat of mixing of eutectics and addition compound

The best of mixing of an eutectic or an addition compound can be

very easily calculated by the following equation and thereby an insight into

the structure of melts in binary eutectics and addition compounds may be

obtained :

(Af h)M = (Af h)exp. - Xi Af hi0 ..(15)

Where fhexp is the heat of fusion of the system determined

experimentally, x, and Af hi° are the mole fraction and heat of fusion,

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

high exothermic heat of mixing. Anthracene-anthracene, phenanthrene-

phenanthrene, naphthalene-naphthalene, picric acid-picric acid, a-naphthol -

a-naphthol and p-toluidine - p-toluidine interactions are very weak as

compared to the arene-picric acid or a-naphthol - p-toluidine interactions.

The exothermic mixing confirms the compound formation in each case,

which is in accordance with the phase-diagram and spectral studies. The

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

 132

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

compound. This indicates that there would be a comparatively weak

interaction in case of eutectics as compared to a strong interaction in the
complex. It is also very interesting that some of the eutectics in these system
have extremely low heats of mixing. This can be explained on the basis of

the possibility of a simple molecular solution instead of weak interactions.

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

considerable enhancement of interaction between the eutectic forming

components due to the presence of 1:1 molecular compound in the eutectic
melt.
Table 47: Heat of Mixing (KJM1)

System Eutectic-1 Eutectic-2 Addition

Compund

Naphthalene-Picric

Acid -0.609 -0.440 -4.182

Anthracene-Picric

Acid -0.889 -1.198 -7.635

Phenanthrene-Picric

Acid -0.496 -0.694 -9.021

a-Naphthol-p-toluidine -0.084 -0.752 -2.886

 133

3.13 Effect of some Parameters Controlling

o the Degree
o of
Undercooling of Pure Components, Eutectics and Addition
Compound
In a number of investigations14,15 into the undercooling of bulk

samples of liquid melts, where the undercooling temperature is determined

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

instantaneous rate of release of the heat of transformation corresponding to

mixing and solidification must exceed the instantaneous rate of heat

withdrawl resulting from the imposed temperature-gradients. Moreover, the

effect of repeated heating and cooling on the number of nucleants

responsible to start the process of solidification, the effect of solute

concentration on growth-rate and the effect of the latent heat of fusion on

equilibrium freezing temperature are such significant factors which would

not leave the degree of undercooling unchanged. The effect of these

parameters on degree of undercooling of the pure components, eutectics and

the addition compound of naphthalene-picric acid, anthracene-picric acid,

phenanthrene-picric acid and a-naphthol - p-toluidine systems have been

studied and the results incorporated in Tables from 27 to 39.

3.14 Effect of cooling rate on undercooling
1 f\
The cooling rate varies with the pure sample or the type of alloy .Since
cooling is mainly, radioactive, the higher melting point compounds have

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

FIG. 3.21: Effect of cooling rate on degree of undercooling of

naphthalene-picric acid system.
 135

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

FIG. 3.22: Effect of freezing cycle number on degree of

undercooling of naphthalene-picric acid system.
 136

* 9 t
UNDERCOOLING (AT)

FIG. 3 .23: Effect of freezing cycle number on degree of

undercooling of anthracene-picric acid system.
 137

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.)

FIG. 3.24: Effect of cooling rate on degree of undercooling of

phenanthrene-picric acid system.
 138

A-----A---- A-
UNDERCOOLING (AT)

ANTHRACENE
PICRIC ACID
PHENANTHRENE-PICRIC
ACID EUTECTIC-1
PHENANTHRENE-PICRIC
ACID EUTECTIC-2
PHENANTHRENE-PICRIC
ACID COMPLEX

FREEZING CYCLE NUMBER

FIG. 3 .25: Effect of freezing cycle number on degree of

undercooling of phenanthrene-pieric acid system.
 139

FIG. 3.26: Effect of cooling rate on degree of undercooling of

a-naphthol-p-toluidine system.
 140

18 O____ q a-naphthol
___ /\ p-toluidine

16 •------ • a-naphthol-p-toluidine eutectic-1

Jk----- A a-naphthol-p-toluidine eutectic-2
□------□ a-naphthol-p-toluidine addition compound
14

12
UNDERCOOLING (A.T)
o
oo
o0 0
'O
oS3

0 1 23 45 67 8 9 10

FREEZING CYCLE NUMBER

FIG. 3.27: Effect of freezing cycle number on degree of

undercooling of a-naphthol-p-toluidine system.
 141

The observations made on these systems indicate that in each case the

undercooling is significantly greater at the faster cooling rate. It can be

explained as the arrest or reversal of cooling rate requires that the

instantaneous rate of release of heat of transformation shall exceed the

instantaneous heat-withdrawal rate resulting from the imposed temperature

gradients. It is clear that the instantaneous rate of release of heat of

transformation (essentially due to solidification) is determined by the

nucleation and the (liquid-solid) volume transformation rates. In the

simplest case, assuming spherical growth and a constant radial growth rate,

the volume rate of growth of a crystal increases as the radius or time

squared, and as such is mainly time-determined and only slightly affected

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

temperature before the transformation rate with its corresponding rate of

evolution of heat, eventually equalizes or even surpasses the rate of heat-

withdrawal. The effect of rate of cooling on undercooling of pure

components, eutectics and the addition compound of each system under

investigation has been given from Fig. 3.23 to 3.26.

3.15 Effect of freezing-cveie number on degree of under cool:

Generally, the maximum degree of undercooling achieved in the melt

depends upon the number of freezing cycles used. The effect of freezing

cycle number on degree of undercooling of pure components, eutectics and

the addition compound of naphthalene-picric acid, anthracene-picric acid,

phenanthrene-picric acid and a-naphthol - p-toluidine systems have been

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

temperature, while on repeated melting and freezing, a reproducible

undercooling could be achieved after certain freezing cycle numbers

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

to start solidification and every cycle removes a fraction of total nucleants

enabling the melt to undergo solidification progressive at a lower

temperature with the increasing cycle number. A consistent undercooling is

achieved when all the nucleants are removed in this way. The removal of

nucleants in case of pure components seems to be easier than those of the

eutectics and the complex.

3.16 Effect of quantity of melt on degree of undercooling

The results from the observations made on the effect of the quantity of the

melt on degree of undercooling of pure components, eutectics and the

addition compound of naphthalene-picric acid, anthracene-picric acid,

phenanthrene-picric acid and a-naphthol - p-toluidine systems have been

given in Tables 29, 32, 35 and 38 respectively. The maximum degree of

undercooling and recalescences attained in these molten systems were

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

the same although, it has a different tendency for different systems. In an

earlier investigation Ohashi et al280 observed a similar dependence of

undercooling on the quantity of melts. According to Kattamis and

 143

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

to the surrounding can be used to show that in a bulk melt recalescence is

sufficient to bring the temperature of the melt to its equilibrium freezing

point. When the melt is in small quantity, the available latent heat may not

be sufficient to raise the temperature of the under cooled liquid to the

equilibrium freezing point, possibly, due to faster conduction and loss of

heat to the surroundings. Additionally, the higher undercooling of smaller

quantity of melt may also be due to relatively less number of nucleants

present as compared to the bulk melt.

3.17 Effect of alloy composition on degree of undercooling

The effect of the composition of alloy on degree of undercooling of

naphthalene-picric acid, anthracene-picric acid phenanthrene-picric acid and

a-naphthol - p-toluidine systems have been shown in Table 39. In the

earlier studies on the nucleation of primary phase in under cooled bulk of

binary alloys, the effect of composition on degree of undercooling was not

adequately considered. The undercooling required for nucleation of the

primary phase was assumed to be independent of alloy composition within

the hypo or hyper-eutectic regions of the phase-diagram. Youdelis and

Iyer232 have recently reported the effect of alloy composition on degree of

undercooling in several binary alloy systems. In our system it was observed

that the undercooling increases as the composition of alloy approaches the

eutectic composition. Our experimental observation can be explained such

as the growth-rate of primary crystal, which primarily depends on the rate of

diffusion of solvent atoms to the crystal-liquid interface, decreases with the

 144

increasing solute concentration. The decreased crystal growth rate resulted

in a correspondingly lower rate of heat evolution so that the melt

undercooled to a greater degree.

Thus, it can be concluded from above studies that the undercooling

temperature for a bulk sample, as determined from the cooling curve, can

not be taken as the temperature at which the nucleation is initiated, but is an

arbitrary value which is a function of cooling rate, quantity of melt, freezing

cycle number and the alloy composition. The effect of these parameters on

degree of undercooling was qualitatively alive but differ quantitatively in

case of each system.

 145

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