EASTERN VISAYAS STATE UNIVERSITY

College of Engineering Technical Report in

Chemical Engineering Department CHE 413 ChE Thermodynamics

1 Technical Report # 1 (☐ First Submission;  Revised Version)

2 Student Name: Gertrude A. Peñalosa; Marygrace S. Progella
3 Instructor: Engr. Joan R. Aligante
4 Date Submitted: January 07, 2019
5

6 ON THE HEAT OF FORMATION OF SOLID

7 ALLOYS
8 Andries R. Miedema 1 and Frank Roelof de Boer 2,*
9 1 Affiliation 1; University of Amsterdam, Amsterdam, Netherlands (1965-1990)
10 2 Affiliation 2; Physics University of Amsterdam, Amsterdam, Netherlands (1992-2003)

11 Keywords: solid alloys; energy effects; chemical potential

12

13 1. Background of the Study

14 Alloying is a process in which two or more metal elements are melted together in a precise
15 combination to form a specific material. This process produces “alloys” which are often preferred
16 over single element metals, particularly for solder preforms, because of their different melting
17 points, specific conductivity attributes or improved thermal expansion values. In microscopic
18 view, the process of alloying involves a charge and energy transfer in their atomic structure which
19 results to a generation or release of heat ; and this mechanism is called as the “heat or enthalpy
20 of formation”
21 Previous study shows that the Wigner-Seitz atomic cell concept was utilized to demonstrate
22 that this model excellently accounts the heat of formation of binary alloys and the exact 27
23 transition metals (Miedema, 1973). The mentioned atomic cell concept assumes that the “volumes
24 of atomic cells of two metals are the same in the volume of the formed binary alloy”. The energy
25 effects are represented into two terms which served as the parameters of the study; the first term
26 (1) is the difference in chemical potential between two types of atoms in an alloys and the second
27 term (2) is the density discontinuity made between the boundary of the dissimilar atoms. These
28 approximations are expressed mathematically as:
29
30 ∆𝐻~[−𝑃𝑒(∆𝜑∗ )2 + 𝑄(∆𝑛𝑤𝑠 )2 ] Eq. 1
31 where P and Q are constants, e is the elementary charge constant, ∆𝜑 ∗ is the change in
32 chemical potential and ∆𝑛𝑤𝑠 is the change in density discontinuity between the boundary of
33 dissimilar atoms.
34 However, the expression formed insufficiently describe the heat of formation of alloys of
35 transition metals. de Boer et.al. (1975), assumed the that surface factor of P and Q are expected to
36 be proportional to something like V2/3m, where Vm is the average molar volume. Nevertheless, this
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College of Engineering Technical Report in
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37 assumption is considered to be cancelled by a density factor, which makes the constant P in the
38 expressed equation as a universal constant.
39 Further, since the second term (∆𝑛𝑤𝑠 ) is bearing a positive sign, its contributes a factor nws-
40 4/3 in the front which changes the equation to be

41 ∆𝐻~[−𝑃𝑒(∆𝜑∗ )2 + 𝑄 ′ 𝑛𝑤𝑠 −4/3 (∆𝑛𝑤𝑠 )2 ] Eq. 2

42 and can be rewritten as:
43 ∆𝐻~[−𝑃𝑒(∆𝜑∗ )2 + 𝑄𝑂 (∆𝑛𝑤𝑠1/3 )2 ] Eq. 3
44 Qualitative and quantitative analysis of data were used to profoundly understand the if
45 alteration of the equation satisfies to these data gathered
46
47 1.1 Statement of the Problem
48 The overall purpose of this study is to demonstrate that the second term is preferably written
49 as Qo (∆nws1/3) in the expressed formula of heat of formation of solid alloys (see Eq.1). It is also
50 aimed to asses if these term resulted to a significant change in the values of shown in Table 1 and
51 2.
52
53 2. Goal/s and Objective/s of the Study
54 The goal of this research project is to amply demonstrate the energy effects in alloys of
55 transition metals between individual atoms.

56 Specifically, the objectives of this study are:

57 1. To quantitively measure the parameters in order to identify if there is a significant change

58 of values in the heat of formation of solid alloys.
59 2. To analyze the sign of Heats of formation through experimental data and binary phase
60 diagrams.
61 3. To identify the relationship of different equations with regards to the heat of formation of
62 solid alloys.

63 3. Theoretical background
64 In the study concerning on the heat of formation of solid alloys, the following relevant
65 theories were adapted and utilized by the researchers to support the entire concept and claims
66 of the study.

67 3.1 Wigner-Seitz Atomic cell concept

68 This concept is deemed crucial in studying crystal solid structure. A Wigner-Seitz cell
69 (or known as primitive cell) is a volume that can fill all of space, without gaps, when translated
70 by lattice vectors. The choice of unit cell is also non-unique, so it is convenient to have a
71 standard for assigning them. Specifically, it describes the volume of space that is closer to that
72 point than any other in the lattice. (Baczewski, 2011).
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73 The Wigner-Seitz atomic cell concept become a basis of assumption for which all volume
74 of two dissimilar atoms of the metals are equal or slightly different to the volume of the formed
75 alloy. This interprets the relationship of the total molar volume to be equal to Vm2/3 and the surface
76 are factor of the positive density continuity to be nws4/3.

77 3.2 Electronegativity parameter for transition metals.

78 In the published study of Miedema (1975), he justified that the electronegativity expresses
79 a scale which is closely related to the experimental work function of pure metals. Using this scale,
80 the alloying behavior of transition metals with non-transition metals are discovered. If the latter
81 have p-electrons, and additional negative term shows up in the heat of formation which does not
82 depend on particular metals considered.

83 3.3 Bruillon zone effect

84 In this study, it is considered. However, it only played a minor role in alloys of heat of
85 transition metals as far as the cohesive energy is concerned; it means that the heat of melting of
86 alloys will be not be much different from that of a mechanical mixture. (de Boer et.al., 1975)

87 4. Research Design & Methods

88 From the goals and objectives stated above, it is clear that the Researchers will restrict to
89 a purely empirical approach in analyzing the relationship of the different equations with regards
90 to the heat of formation of solid alloys. Herein, are the various experimental information
91 concerning the parameters needed in the relationship for the heats of formation of alloys which
92 will accurately reproduce the alloying behavior of the group of alloys considered. Specifically,
93 this study will be completed using the over-all research procedures shown in the flow diagram
94 below:

95

96

97

98

99
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College of Engineering Technical Report in
Chemical Engineering Department CHE 413 ChE Thermodynamics

100 5. Results and Discussions

101 From the empirical approach of analyzing related data and studies, the Researchers have
102 come up the following Results and Conclusions stated below:

103 First, the energy effects in alloys of transition metals can be described in terms of the
104 interaction between the individual atoms. According to Wigner-Seitz concept of atomic cells that,
105 to a first approximation (Fig. l (a), (b)) the volumes of the atomic cells of the two metals, A and B,
106 are assumed to be the same in the alloy and in the pure metals. Since a change in the shape of a
107 Wigner -Seitz cell can be brought about at the cost of very little energy (at constant volume), the
108 energy effect of alloying would be close to zero in this approximation. However, the boundary
109 conditions between dissimilar cells change to different effects.

110 The energy effect is derived from two contributions; a negative one, arising from the
111 difference in chemical potential, 𝜑 ∗ , for electrons at the two types of atomic cells, and a second
112 term, which reflects the discontinuity in the density of electrons, nws, at the boundary between
113 dissimilar atomic cells. Expressed as a formula,

114 ∆𝐻~[−𝑃𝑒(∆𝜑 ∗ )2 + 𝑄(∆𝑛𝑤𝑠 )2 ] Eq. 1

115 The first is that, in general, there will be a discontinuity in the density of electrons nws at
116 the boundary between dissimilar cells, if these are taken to be equal to those in the pure
 EASTERN VISAYAS STATE UNIVERSITY
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117 constituent metals. This density discontinuity has to be smoothed; since the original densities at
118 the cell boundary of the pure metals correspond to an energy minimum for each of them, the
119 removal of this discontinuity will lead to a positive contribution to the energy of alloying. The
120 positive contribution, to a first approximation, can be expected to be proportional to (∆𝑛𝑤𝑠 )2 .

121 Secondly, there will be a difference in the chemical potential for electrons in the two types
122 of pure metal cells. However, the chemical potential, 𝜑 ∗ , cannot vary in an alloy. Hence, there
123 will be some transfer of charge, resulting in a negative contribution to the heat of formation of
124 the alloy. To a first approximation this energy effect will be proportional to (∆𝜑 ∗ )2 . This is
125 analogous to the situation in which two macroscopic pieces of metal are brought into contact,
126 which leads to an electric dipole layer with an energy proportional to −(∆𝜑𝑒𝑥𝑝 )2 where 𝜑𝑒𝑥𝑝 is the
127 work function. Addition of the two energies gives:

128 ∆𝐻~[−𝑃𝑒(∆𝜑 ∗ )2 + 𝑄(∆𝑛𝑤𝑠 )2 ] Eq. 1

129 Here ∆H represents the enthalpy of formation per gram atom of alloy, e is the elementary
130 charge while, as was demonstrated in paper I, the proportionality factors P and Q are constants
131 for a given group of alloy systems.

132 Information concerning the sign of ∆H is obtained from binary phase diagrams. Since, for
133 inter-metallic compounds quite generally, ∆H and ∆G are not very different (i.e., entropy effects
134 are relatively unimportant), it has been assumed in paper I that ∆H has a negative sign for all
135 binary systems in which stable inter-metallic compounds have been observed. On the other hand,
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136 ∆H is taken as positive if there are no compounds in a system, while, in addition, the mutual solid
137 solubilities are smaller than 10 at %.

138 The positive term in relationship (1) should also contain the same surface- area factor.
139 Here, too, additional effects must be considered, but now the two effects do not cancel. It
140 transpires that, rather than being simply proportional to (∆𝑛𝑤𝑠 )2 , the positive energy
−4/3
141 contribution contains a factor, 𝑛𝑤𝑠 , in front. As a result,

142 ∆𝐻~[−𝑃𝑒(∆𝜑 ∗ )2 + 𝑄 ′ 𝑛𝑤𝑠 −4/3 (∆𝑛𝑤𝑠 )2 ] Eq. 2

143 and can be rewritten as:
144 ∆𝐻~[−𝑃𝑒(∆𝜑 ∗ )2 + 𝑄𝑂 (∆𝑛𝑤𝑠1/3 )2 ] Eq. 3
145 Clearly, from an empirical point of view there is no basic difference between the relationships
146 (1) and (3), except that ∆𝑛𝑤𝑠 is replaced by ∆𝑛𝑤𝑠 1/3 . Nevertheless, the present approach turns out
147 to have an important advantage, not only because now, a value for P and Qo can be estimated
148 from basic physical considerations, but also empirically. It transpires that, for solid or liquid
149 alloys of two transition metals and of transition and alkali- or alkaline-earth metals, or for liquid
150 alloys of two non-transition metals, the empirical value for the ratio of the proportionality
151 constants P and Q, is always the same.

152 Finally, we may recall the result of paper I for alloys of a transition metal with one of the
153 typical p-electron-type metals, Al, Ga, In, Tl, Sn, Pb, Sb or Bi. It was found that
4
154 ∆𝐻~[−𝑃𝑒(∆𝜑 ∗ )2 + 𝑄 ′ 𝑛𝑤𝑠 −3 (∆𝑛𝑤𝑠 )2 − 𝑅] Eq. 2.1

155 where R represents a large contribution that it was suggested arose from a more effective d-p
156 hybridization energy (relative to the pure d-metal) that is gained when a d-type transition metal
157 acquires p-electron-type neighboring atoms. In this paper (and also in the paper [3] on liquid
158 alloys of d-metals and p-metals) the relationship (4) becomes replaced by:
1
159 ∆𝐻~[−𝑃𝑒(∆𝜑∗ )2 + 𝑄𝑂 (∆𝑛𝑤𝑠 3 )2 − 𝑅] Eq. 3.1
160 On the other hand, the accuracy of the description of experimental ∆H values is sufficiently
161 good to show that R has a (slightly) different value depending on the valency of the p-metal. R
162 increases regularly from the divalent metals, Zn, Cd, Hg, through the trivalent metals, Al, Ga, In,
163 Tl and the tetravalent metals Si, Ge, Sn, Pb, to the pentavalent metals, Sb and Bi. As a result, the
164 description of, and predictions as to the heat of formation of, alloys of transition metals and of p-
165 metals will also acquire quantitative interest.

166 It is found that a somewhat more accurate representation can be obtained (i.e., smaller
167 number of positive signs in the region where ∆H should be negative and vice-versa) if the
168 “constant” R is allowed to be systematically different for metals of different valency. The ratio
169 Qo/P is the same as before; R/P varies from 1.4 eV2 for the divalent metals, to R/P = 1.9 eV2 for the
170 trivalent metals, 2.1 eV2 for Sn and Pb, and R/P = 2.3 eV2 for the pentavalent metals Sb and Bi.
171 Alloys of transition metals with divalent Mg and Be, if analyzed in a similar way, indicate a still
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172 smaller value of R than that for Zn, Cd and Hg. We have found, on analyzing absolute ∆H values
173 rather than just the sign of ∆H, that R/P = 0.4 eV2.

174 For the sake of clarity we may summarize the empirical results obtained in this Section.
175 The heat of formation of binary alloys based on one or two transition metals can be described by
176 relationship (5). If the partner metal is also a transition metal, or is one of the metals Li, Na, K, Rb,
177 Cs, Cu, Ag, Au, Ca, Sr or Ba, the value of the empirical constant, R, is zero. If the second metal is
178 Be or Mg, R/P equals 0.4 eV2, whilst if it is Zn, Cd or Hg, R/P equals 1.4. If the partner metal is one
179 of the trivalent, tetravalent or pentavalent non-transition metals, R/P equals 1.9, 2.1 or 2.3 eV2,
180 respectively. For liquid alloys the R values are reduced by approximately a factor of 0.73. In the
181 case of alloys of the noble metals Cu, Ag or Au with the p metals, there is an additional reduction
182 factor for R of 0.2. For alloys of two non-transition metals, including alkaline, alkaline-earth and
183 all other polyvalent non-transition metals, relationship (3) with R = 0 applies to the liquid state.
1
184 Since all six binaries have( ∆𝜑 ∗ , ∆𝑛𝑤𝑠 3 ) values close to the straight line representing ∆H = 0, the
185 discrepancies are not serious. The slope of the line corresponds to Qo/P = 9.4 in units eV2 per
186 (density unit)2/3, where the units for the electron densities are those of Table 1.

187 The ratio of the two proportionality constants, Qo/P, is the same for all alloy systems and,
188 as will be found later when absolute values of ∆H are analyzed, neither this ratio, nor the
189 individual values of Q, and P depend to any great extent on the group of alloys considered.

190 We shall restrict ourselves to a purely empirical approach. Our aim is to demonstrate that
191 relations (3) and (5) are useful and account for the experimental information on heats of formation
192 of alloys.
1
193 In Table 1 are collected our selected values for 𝜑 ∗ and ∆𝑛𝑤𝑠 3 of the metallic elements. As
194 in paper I, the two parameters have been derived, in principle, from experimental data on the
195 work function, 𝜑 ∗ , the bulk modulus, B, and the molar volume, Vm , of pure metals. In spite of
196 this there are some differences between the values of 𝜑 ∗ and nws in this paper and of those in
197 paper I. The reason for this is that the ultimately selected values for the two parameters have been
198 obtained from a best-fit to relationship (3) while in paper I relationship (1) was used.

199 In Fig. 1, the energy effect that accompanies alloying has been introduced as arising,
200 primarily, from the change in boundary conditions upon the transfer of an atomic cell from a pure
201 metal to an alloy. This picture implies that the total area of the contact surface between dissimilar
202 atoms is the relevant quantity. For this reason, it is useful to introduce the concept “surface
203 concentration”, a term which is analogous to “volume concentration”. For two metals, A and B,
204 in an alloy with atomic concentrations, cA and cB, and molar volumes VA and VB the surface
205 concentrations 𝑐𝐴𝑠 and 𝑐𝐵𝑠 are defined by:
2 2 2
206 𝑐𝐴𝑠 = 𝑐𝐴 𝑉𝐴3 /(𝑐𝐴 𝑉𝐴3 + 𝑐𝐵 𝑉𝐵3 ), Eq. 4
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2 2 2
207 𝑐𝐵𝑠 = 𝑐𝐵 𝑉𝐵3 /(𝑐𝐴 𝑉𝐴3 + 𝑐𝐵 𝑉𝐵3 ). Eq. 5

208 For regular liquid or solid solutions the concentration dependence of ∆H will contain the
209 product 𝑐𝐴𝑠 𝑐𝐵𝑠 . For ordered compounds the area of contact between dissimilar cells will be larger
210 than the statistical value. Here, the factor can be found empirically by collecting experimental ∆H
211 values for those binary systems for which a number of ordered compounds has been studied.
212 Also, the fact that near the equiatomic compositions, the ordering energy of alloys, quite
213 generally, has been found by measurement to be equal to l/3 of the total (negative) heat of
214 formation, offers a clue on the difference in the concentration dependence of ∆H between ordered
215 compounds and regular solutions. A simple analytical expression that approximately reproduces
216 this (derived empirically) difference is:

217 𝑓(𝑐𝐴𝑠 𝑐𝐵𝑠 )𝑜𝑟𝑑𝑒𝑟𝑒𝑑 = 𝑐𝐴𝑠 𝑐𝐵𝑠 [1 + 8(𝑐𝐴𝑠 𝑐𝐵𝑠 )] Eq. 6

218 Considerations on the physical origin of the two terms in relation (3) indicate that in
219 addition to the above function, 𝑓(𝑐𝐴𝑠 𝑐𝐵𝑠 ) there is another factor, 𝑔(𝑐𝐴 , 𝑐𝐵 ), that varies somewhat
220 with the relative concentration of the two metals. As a result, absolute values for ∆H can be
221 derived from:
∆𝐻 ∗ 2 ′ 2
222 = 𝑓(𝑐𝐴𝑠 , 𝑐𝐵𝑠 ) 𝑔(𝑐𝐴 , 𝑐𝐵 )[−𝑃𝑒(∆𝜑 ) + 𝑄 𝑛𝑤𝑠 −4/3 (∆𝑛𝑤𝑠 ) ] Eq. 7
𝑁𝑜

223 No is Avogadro’s number, AH is the heat of formation per gram atom of alloy while
224 g(c*,ca) is:
2 2 2 2
225 𝑔(𝑐𝐴 , 𝑐𝐵 ) = 2(𝑐𝐴 𝑉𝐴3 + 𝑐𝐵 𝑉𝐵3 )/(𝑉𝐴3 + 𝑉𝐵3 ) Eq. 8

226 Values for Vm2/3 for pure metals, needed in the calculations, have been included in Table
227 1 (see Table 1). The comparison between experimental and calculated ∆H values for alloys of two
228 transition metals is made in Table 2. (see Table 2)

229 We have amply demonstrated that energy effects in alloys of transition metals can be
230 described in terms of the interactions between individual atoms. There are three contributions to
231 the alloying enthalpy, the first representing the difference in electronegativity, the second
232 reflecting the difference in density of electrons at the boundary between dissimilar atoms, and
233 the third term representing an additional hybridization energy that occurs if transition metals are
234 alloyed with polyvalent non-transition metals.
 EASTERN VISAYAS STATE UNIVERSITY
College of Engineering Technical Report in
Chemical Engineering Department CHE 413 ChE Thermodynamics

235
 EASTERN VISAYAS STATE UNIVERSITY
College of Engineering Technical Report in
Chemical Engineering Department CHE 413 ChE Thermodynamics

236