Why corrosion by CO2 is unstoppable? Please share your experience and views.

Corrosion by CO2 once takes off can only stop when supply of CO2 is terminated. Condensate lines
and oil pipe lines are worst victims.

Mode CO2 of corrosion is localised redox pitting . The film formation characteristics and
morphology of CO2 systems significantly influences the localized/pitting corrosion behaviour of
exposed carbon steel materials [NACE]. Pitting is one of the most destructive and insidious forms of
corrosion. It causes equipment to fail because of perforation with only a small percent weight loss
of the entire structure. It is often difficult to detect pits because of their small size and because the
pits are often covered with corrosion products.

CO2 pitting corrosion is one of the main modes of corrosion corrosion and the most prevalent
factors contributing to the damage of metal materials during oil and gas well exploitation and
transportation worldwide [NACE]. In the oil and gas industry, carbon dioxide corrosion is known as
sweet corrosion.

Research has shown that CO2 corrosion is caused by a series of complex physical and chemical
processes that are influenced by temperature, CO2 concentration and pH.

How it happens?

Formation of carbonic acid in water

It is not a spontaneous reaction. ΔG = +103.72 kJ at 25 degc / 1 atm pr.

Explanation

A reaction becomes non spontaneous when, ΔG is positive.

ΔG [Free energy change] = ΔH – TΔS,

Enthalpy ΔH of this reaction is 2.20 kJ (endothermic), the entropy change ΔS of the reaction is -
340.49 J/K (negative), the reaction is going from 2 moles of reactants to 1 mole product, that is from
a more disordered state at reactants to more ordered state at product and that makes entropy
change negative. Big negative entropy change, - ΔS makes this reaction unviable. ΔG = +103.72 kJ
at 298.15 K or 25 degc and 1 atm pressure. This is the fundamental step to understand what
follows in the entire process of CO2 corrosion.

How cabonic acid causes corrosion?

Corrosion drivers

This is the equilibrium chain of CO2 in water which is controlled by concentration, temperature and
pH.

CO2(aq) + H2O(l) < = > H2CO3(l) < = > HCO3-(aq) + H+

Role of concentration – Push reaction forward. Carbonic acid formation at 25 degc / 1 atm
pressure is not spontaneous, ΔG = +103.72 kJ. Pco2 [CO2 partial pressure] is a key driver

pH - H+ ion concentration drives corrosion

Role of temperature – Reduction of activation energy of corrosion reaction. The activation energy
of a chemical reaction is closely related to its rate. Smaller the Ea faster the reaction.

The terminal H+ ion is on the lookout for electrons, it oxidises metal and make metal to loose
electrons and get itself reduced to H2 gas

M [ metal] ------ > M++ + 2e [oxidation]

2H+ + 2e = H2 gas [reduction]

As at tail end H+ ions get consumed in corrostion reaction, more carbonic acid goes in water and
this reaction goes on until CO2 supply at front end has been terminated.

CO2 corrosion can be reduced by the formation of a thin film (nm) of organic inhibitors on the
surface of the steel, or a protective corrosion layer. Filming amines protect condensate systems
from carbon dioxide.