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Railsback's Some Fundamentals of Mineralogy and Geochemistry

Bowen's Reaction Series III: Melting temperatures of oxides


This page is a step on the road to understanding for Rb+) to upper right (z/r = 45 for N5+). The highest
Bowen's Reaction Series, the subject of a series of values of Tm for the oxides are thus those of the oxides
pages in this book. Pages IV and V will finish the job. of cations of intermediate ionic potential, rather than
The diagram at left is a bit of the periodic table. cations of low or high ionic potential. The reasons for
Superposed on it are contours showing the melting that relationship are shown below: low ionic potential
temperatures (Tm) of the oxides of the cations in this only allows weak electrostatic bonding to O2-, and high
part of the table. Tm is greatest for the swath of ionic potential causes repulsions between cations, but
cations from Mg2+ to Th4+. intermediate ionic potential hits the happy medium of
On this part of the periodic table, ionic potential strong bonds without cation-cation repulsions.
(charge ÷ radius) increases from lower left (z/r = 0.67
Contours of ionic potential:
Melting T(K) of oxides of hard cations Li + Be2+ B 3+ C 4+ N 5+
32
+ 2+ 4+ 5+ ss-
Li Be B 3+ C N h o f cro ow
Na + Mg2+ Al 3+ Si 4+ P5+ S 6+
16
1700 2681 723 216 Pat ion bel
t K+ Ca2+ Sc3+ Ti 4+ V 5+ Cr 6+
sec
500
Rb+ Sr 2+ Y 3+ Zr 4+ Nb 5+ Mo6+
+ 2+ 4+ 5+ 6+
Na Mg Al 3+ Si P S charge
1193 3125 2345 1996 855 290 radius Cs + Ba2+ La 3+ Hf 4+ Ta5+ W 6+
1 2 4 8
Conceptual model of the
+ 2+ 3+ 4+ 5+ 6+ behavior of oxides of hard
K Ca Sc Ti V Cr
3200 2103 943 (and intermediate) cations
Li N
Cations
10 1Å
00 H+

+
Rb Sr 2+ Y 3+ Zr 4+ Nb5+ Mo6+
673 2938 3123 1785 1074
High z/r
Strong
Rb O2– bonds, but
+
Cs Ba2+ La 3+ Hf 4+ Ta 5+ W 6+ Low z/r
Intermediate cation-cation
repulsion
1500

2286 2580 3173 2058 1745 z/r


Weak cation- Strong cation-
2000

oxygen bonds oxygen bonds Thus less


1500
200

2500

2500

stable
3000

300

Th 4+
0

Thus less Thus stable solids


stable solids solids
0

3493
Mleting temperature (°C) of

3000 Melting temperatures of


oxides of hard cations

oxides of hard cationsIf we make a profile across


2500
the periodic table, we can
2000 construct the diagram at lower
1500 Dry left, where melting temperature
of the oxides is plotted against
1000 ionic potential. With this
Wet
500 Fe2+ Fe3+ Ti4+ diagram, we can proceed to
K+ Na+ Ca2+ Mg2+ Cr3+ Zr4+ Al3+ Si4+
Bowen's Reaction Series IV,
0 1 2 3 4 5 6 7 8 9 10 where we will plot the minerals
Low ionic potential Intermediate ionic potential High ionic potential
(weak cation-O 2- 2-
(Stable cation-O frameworks) (cation-cation repulsion) of Bowen's Reaction Series on
bonds) this diagram.
Ionic potential (charge ÷ radius) of cations
LBR BRSIII05 1/2007

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