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Diagram Ellingham
Diagram Ellingham
Ellingham diagrams are a particular graphical form of the principle that the thermodynamic feasibility of a
reaction depends on the sign of ΔG, the Gibbs free energy change, which is equal to ΔH − TΔS, where ΔH is
the enthalpy change and ΔS is the entropy change.
Simple Ellingham diagram for high temperature (0°C – 2500°C) oxidation of several metals and carbon
The Ellingham diagram plots the Gibbs free energy change (ΔG) for each oxidation reaction as a function of
temperature. For comparison of different reactions, all values of ΔG refer to the reaction of the same
quantity of oxygen, chosen as one mole O (1⁄2 mol O2) by some authors[2] and one mole O
2 by others.[3] The diagram at right refers to 1 mole O, so that for example the line marked Cr2O
3 shows ΔG for the reaction 2/3 Cr(s) + 1⁄2 O2(g) → 1⁄3 Cr2O
3(s), which is 1⁄3 of the molar Gibbs energy of formation ΔGf°(Cr2O3, s).
In the temperature ranges commonly used, the metal and the oxide are in a condensed state (liquid or solid),
and oxygen is a gas with a much larger molar entropy. For the oxidation of each metal, the dominant
contribution to the entropy change (ΔS) is the removal of 1⁄2 mol O
2, so that ΔS is negative and roughly equal for all metals. The slope of the plots dΔG/dT = − ΔS is therefore
positive for all metals, with ΔG always becoming more negative with lower temperature, and the lines for all
the metal oxides are approximately parallel. Since these reactions are exothermic, they always become
feasible at lower temperatures. At a sufficiently high temperature, the sign of ΔG may invert (becoming
positive) and the oxide can spontaneously reduce to the metal, as shown for Ag and Cu.
For oxidation of carbon, the red line is for the formation of CO: C(s) + 1⁄2 O
2(g) → CO(g) with an increase in the number of moles of gas, leading to a positive ΔS and a negative slope.
The blue line for the formation of CO2 is approximately horizontal, since the reaction C(s) + O2(g) → CO
2(g) leaves the number of moles of gas unchanged so that ΔS is small.
As with any chemical reaction prediction based on purely thermodynamic grounds, a spontaneous reaction
may be very slow if one or more stages in the reaction pathway have very high activation energies EA.
If two metals are present, two equilibria have to be considered. The oxide with the more negative ΔG will be
formed and the other oxide will be reduced.
SALIENT FEATURES
1. Curves in the Ellingham diagrams for the formation of metallic oxides are basically straight lines
with a positive slope. The slope is proportional to ΔS, which is fairly constant with temperature.
2. The lower the position of a metal's line in the Ellingham diagram, the greater is the stability of its
oxide. For example, the line for Al (oxidation of aluminium) is found to be below that for Fe
(formation of Fe2O3).
3. Stability of metallic oxides decreases with increase in temperature. Highly unstable oxides like Ag
2O and HgO easily undergo thermal decomposition.
4. The formation free energy of carbon dioxide (CO
2) is almost independent of temperature, while that of carbon monoxide (CO) has negative slope and
crosses the CO
2 line near 700 °C. According to the Boudouard reaction, carbon monoxide is the dominant oxide of
carbon at higher temperatures (above about 700 °C), and the higher the temperature (above 700 °C)
the more effective a reductant (reducing agent) carbon is.
5. A reduced substance (such as a metal), whose Gibbs free energy of formation is lower on the
diagram at a given temperature, will reduce an oxide whose free energy of formation is higher on the
diagram. For example, metallic aluminium can reduce iron oxide to metallic iron, the aluminium
itself being oxidized to aluminium oxide. (This reaction is employed in thermite.)
6. The greater the gap between any two lines, the greater the effectiveness of the reducing agent
corresponding to the lower line.
7. The intersection of two lines implies an oxidation-reduction equilibrium. Reduction using a given
reductant is possible at temperatures above the intersection point where the ΔG line of that reductant
is lower on the diagram than that of the metallic oxide to be reduced. At the point of intersection the
free energy change for the reaction is zero, below this temperature it is positive and the metallic
oxide is stable in the presence of the reductant, while above the point of intersection the Gibbs
energy is negative and the oxide can be reduced.
Reducing agents
In industrial processes, the reduction of metal oxides is often effected by a carbothermic reaction, using
carbon as a reducing agent. Carbon is available cheaply as coal, which can be rendered to coke. Moreover,
when carbon reacts with oxygen it forms the gaseous oxides carbon monoxide and carbon dioxide, so the
thermodynamics of its oxidation is different from that for metals: its oxidation has a more negative ΔG with
higher temperatures (above 700 °C). Carbon can thus serve as reducing agent. Using this property, reduction
of metals may be performed as a double redox reaction at relatively low temperature.
In iron ore smelting, haematite gets reduced at the top of the furnace, where temperature is in the range 600
– 700 °C. The Ellingham diagram indicates that in this range carbon monoxide acts as a stronger reducing
agent than carbon since the process
2 CO + O
2 → 2 CO
2
In the upper part of the blast furnace, haematite is reduced by CO (produced by oxidation of coke lower
down, at higher temperatures) even in the presence of carbon – though this is mainly because the kinetics for
gaseous CO reacting with the ore are better.
Thermite reaction proceeding for a railway welding. Shortly after this, the liquid iron flows into the mould
around the rail gap
The Ellingham curve for aluminium lies below the curves of most metals such chromium, iron, etc. This fact
indicates that aluminium can be used as the reducing agent for oxides of all these metals. This result is
illustrated as follows:
The free energies of formation of chromium(III) oxide and aluminium oxide per mole of oxygen consumed
are -540kJ and -827kJ respectively. The processes are:
(1)
(2)
So aluminium oxide is more stable than chromium oxide (at least at normal temperatures, and in fact all the
way up to the decomposition temperatures of the oxides). Since the Gibbs free energy change is negative,
aluminium can reduce chromium oxide.
Suhu adalah ukuran yang menyatakan energi panas tersimpan dalam suatu benda. Benda bersuhu tinggi
berarti memiliki energi panas yang tinggi, begitu juga sebaliknya. Kalor adalah perpindahan energi panas
yang terjadi dari benda bersuhu yang lebih tinggi ke benda bersuhu lebih rendah.
Celcius (oC)
Reamur (oR)
Fahrenheit (oF)
Kelvin (K)
Dimana Q adalah banyak kalor (J), m adalah massa benda (Kg), c adalah kalor jenis (J/KgoC) dan adalah
perubahan suhu (oC). Apabila benda mengalami perubahan wujud, maka jumlah energi yang digunakan
tersebut dihitung dengan rumus m.L, dimana L adalah kalor jenis perubahan wujud zat. Satuan ukur kalor
adalah kalori, dimana satu kalori adalah jumlah energi panas yang dibutuhkan untuk menaikkan suhu 1 gram
air sebesar 1oC. 1 Kalori disetarakan dengan 4.2 Joule.
Perpindahan Panas
Perpindahan panas dapat dibagi menjadi tiga jenis berdasarkan medium perantaranya. Tiga jenis
perpindahan panas tersebut adalah konduksi, konveksi, dan radiasi.
1. Konduksi
Konduksi berarti energi panas bergerak tanpa disertai pergerakan permanen medium yang menjadi
penghantar panas. Contoh konduksi adalah rambatan panas pada material logam seperti besi, kawat, dan
alumunium. Pada level molekuler, konduksi terjadi karena adanya tubrukan antara molekul berkecapatan
lebih tinggi dengan molekul berkecepatan lebih rendah. Hal ini menghasilkan peningkatan energi kinetik
molekular yang selanjutnya meningkatkan suhu.
2. Konveksi
Konveksi adalah perpindahan panas yang terjadi seiring dengan perpindahan zat perantara atau medum.
Contoh dari konveksi adalah pendinginan ruangan dengan AC dan pemanasan air. Pada level molekular,
peningkatan suhu akan berpengaruh pada peningkatan volume dan juga kerapatan medium. Medium yang
lebih renggang akan bergerak ke bawah, dan medium yang rapat bergerak ke atas. Medium yang lebih
renggang adalah medium yang bersuhu lebih rendah, sebaliknya medium lebih rapat berarti suhu lebih
tinggi. Pergerakan antar medium inilah yang mengakibatkan perpindahan panas.
3. Radiasi
Radiasi adalah penghantaran energi panas tanpa dibutuhkan penghantar. Panas ditransmisikan dengan emisi
gelombang elektromagnetik. Pada level molekular, radiasi panas terjadi karena pergerakan acak momentum
dan atom akibat radiasi elektromagnetik. Setiap benda akan mengeluarkan radiasi termal, bergantung dari
panas yang dimiliki. Semakin panas objek tersebut makan semakin besar radiasinya. Salah satu contoh
radiasi panas adalah perpindahan energi panas dari matahari ke bumi dan benda-benda antariksa lainnya.
Ketiga jenis perpindahan panas tersebut dapat terjadi sekaligus pada suatu proses pemanasan. Contohnya
adalah proses memanaskan panci berisi air di atas kompor seperti pada gambar berikut. Rambatan panas api
dari kompor ke panci adalah proses radiasi, kemudian air yang panas di bagian bawah panci akan bergerak
ke atas bertukar posisi dengan air di bagian atas menghasilkan transfer panas melalui konveksi, dan panas
yang terdapat di pemegang panci yang terbuat dari logam dapat dihantarkan ke tangan melalui proses
konduksi.
Asas Black
Asas Black adalah hukum yang menyatakan bahwa untuk semua pertukaran energi panas (kalor), maka
kalor yang diterima materi bersuhu lebih rendah akan sama besar dengan kalor yang dilepas oleh materi
bersuhu lebih tinggi. Secara matematis, Asas Black dinyatakan sebagai berikut.
Jika terdapat dua materi dengan suhu berbeda dicampurkan menjadi satu, asas black dapat digunakan untuk
mengetahui suhu akhir campuran. Penerapannya secara matematis adalah sebagai berikut.
Keterangan:
Kratos mencampur 4 kg air bersuhu 100oC dengan 8 kg air bersuhu 50oC. Berapa suhu akhir campuran?
Jawab
Diketahui:
m1 = 4 Kg
m2 = 8 Kg
c1 = c2 = c
T1 =100 oC
T2 = 50 oC