E-pH Diagram

(Pourbaix Diagram)
Asep Ridwan Setiawan
 Pendahuluan
• Diagram E-pH diagram menunjukan reaksi dan
produk yang diperoleh pada kesetimbangan
elektrokimia. Diagram ini dikenal jg dengan nama
Diagram Pourbaix.
• Pada dasarnya ada 4 daerah pada diagram
pourbaix, yaitu daerah oxidizing (asam), oxidizing
(basa), reducing (asam) dan reducing (basa)
• Diagram ini menunjukkan pada kondisi apa (E dan
pH) logam akan aktif terkorosi, pasif, dan Immun.
 Limit kestabilan air
a) O2 + 4H+ + 4e = 2H2O E0 = +1.23V
Eh = 1.23 – 0.059 pH (at Po2 =1)
b) 2H+ + 2e = H2 E0 = 0.00V
Eh = 0-0.059 pH (at PH2 = 1)

Kesetimbangan elektrokimia diatas

diplot pada gambar disamping.
Diatas garis oksiggen, reaksi
pembentukan O2 terjadi. Sedangkan
dibawah garis hidrogen, reaksi
pembentukan H2 terjadi. Air akan
stabil diantara dua garis tersebut.
 Fakta diagram kestabilan air
• Pada larutan netral atau basa (alkaline), reaksi
dibawah ini bisa terjadi :
1. 2H2O + 2e = H2 + 2OH-
2. O2 + 2H2O + 4e = 4OH-
• Reaksi elektrokimia berupa evolusi hidrogen
mewakili peristiwa dekomposisi air.
• Pada potensial yang lebih positif, reaksi reduksi
oksigen atau oksidasi air terjadi.
• Kemiringan dari kedua garis tsb adalah 59 mV/pH.
Three types of lines in the diagram
a) Those depending only on Eh, but independent of
pH (Horizontal to the X-axis).
b) Those dependent only on pH, but independent of
Eh (Vertical to the X-axis).
c) Those dependent on Eh and pH (Slanted with
definite slopes).
• The above types of reactions and general effects
of Eh and pH on redox reactions (oxidation,
reduction) are illustrated in Fig. 5.3.
Diagram Pourbaix utk Fe
Diagram Pourbaix utk Al

corrosion passivation
corrosion

immunity
Diagram Pourbaix utk Mg
 LIMITATIONS OF POURBAIX DIAGRAMS

• Pourbaix diagrams are based on thermodynamic data, they

convey no information on rates of reaction — that is, whether
any possible reaction proceeds rapidly or slowly when the
energy changes are favorable.
• The data indicate the conditions for which diffusion - barrier
films may form on an electrode surface, but they provide no
measure of how effective such barrier films may be in the
presence of specific anions, such as SO42− or Cl− .
• Similarly, they do not indicate the detailed conditions under
which nonstoichiometric metal compound films are possible;
some of these films are important in determining observed
corrosion rates.
 LIMITATIONS OF POURBAIX DIAGRAMS
• However, the diagrams do clearly outline the nature of
the stoichiometric compounds into which any less
stable compounds may transform whenever
equilibrium is achieved.
• Conventional Pourbaix diagrams do not include alloys;
for example, the corrosion of iron – nickel alloys cannot
be accurately predicted by superimposing conventional
Pourbaix diagrams for iron and nickel [5] .
• With these limitations, the diagrams usefully describe
the equilibrium status of a metal either as immersed in
acids or alkalies or when a given potential is impressed
on it.