Corrosion for Engineers

Course: ENGR 4610
M.H. Kaye

Winter

Corrosion is the destructive attack of a metal by chemical or electrochemical reaction with its environment. Thermodynamics of Corrosion • Equilibrium constants • Basic thermodynamic relationships • H, G, S, Cp • Gibbs free energy • Free energy of formation

Winter

Corrosion For Engineers

ENGR 4610 - 2

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Not spontaneous 0 it requires heat. the degree of disorder in a system A chemical reaction is favoured when ∆G < 0. ∆S > 0 A chemical reaction is not favoured when ∆G > 0. i.3 - .. the chemical energy of the system Corrosion For Engineers ENGR 4610 . the chemical heat in a reaction S = Entropy. ∆S < 0 G = H – TS Winter the Gibbs Free Energy. i. i.e. Spontaneous < 0 it releases heat. i.. Equilibrium entropy decreases. ∆H > A chemical reaction is not favoured when the ∆G = 0.e.Chemical Thermodynamics H = Enthalpy.e. ∆H A chemical reaction is favoured when the entropy increases..e..

Standard Free Energy of Formation = ∆Gf° oxidation reaction Consider the generalized reaction: xM + yO2  MxO2y Since the free energy is a state function.(x∆Gf(M) + y∆Gf(O2)) = ∆Gf(MxO2y) 0 Winter Corrosion For Engineers ENGR 4610 .4 - . That is: 0 ∆Greac = ∆Gf(MxO2y) . we can calculate the change in free energy from the free energy of the initial and final states.

363 213.05 5.806 -394.53 6.287 235.03 29.36 Winter Corrosion For Engineers ENGR 4610 .EXAMPLE Consider the reaction: C(s.769 9.187 225.636 0 8.35 208.5 - .0 kJ/mol C(s.501 220.063 12.298 kJ/mol H°298-H°0 S°298 Cp.413 213.298 kJ/mol 0 0 -393.298 500K 700K 1000K kJ/mol J/mol/K J/mol/K J/mol/K J/mol/K J/mol/K 0 1.11 218. graphite) + O2(g)  CO2(g) We can look up the basic thermodynamic values for the reactants and products.887 9.51 ∆ G°f . graphite) O2 CO2 0 0 -393.14 ∆ H°f .74 8. -(G°T-H°298)/T ∆ H°f .68 205.64 37.

298 500K 700K 1000K ∆ H°f .64 -394.806 ∆Greac = ∆Gf(CO2) = -394.298 H°298-H°0.063 12.14 CO2(g)-393.05 5.363 213.769 -393.36 37. this reaction is spontaneous and graphite is unstable in oxygen.0 ∆ H°f . graphite) f .00205.413 213. Winter Corrosion For Engineers ENGR 4610 . graphite) + O2(g)  CO2(g) From this table.00 kJ/mol kJ/mol kJ/mol kJ/mol J/mol/K J/mol/K J/mol/K J/mol/K J/mol/K 0 0 0 1.51 -394.03 0 0 0 8.36 9.287 235. we can extract the free energy of reaction: Element ELEMENT ∆Gf° / kJ•mol-1 -(G°T-H°298)/T C(s.6 - .53 6.35 208.11 218.68 29.636 O2(g) 0.EXAMPLE C(s.298 ∆ G° 0 S°298 C(s.74 8.887 9. graphite) O2 CO2 Cp.501 220.187 225.36 kJ•mol-1 At room temperature.

Winter Corrosion For Engineers ENGR 4610 .7 - .

The free energy values are determined for a constant temperature and pressure The data are for the reaction at room temperature These are the normal conditions for most chemical reactions studied Temperature dependence? Winter Corrosion For Engineers ENGR 4610 .8 - .

S is the entropy.Temperature dependence Recall the definition of Gibbs free energy: G = H .TdS Recall that: dH = CpdT and dS = (Cp/T) dT dG = -SdT Winter Corrosion For Engineers ENGR 4610 .SdT .9 Cp is the heat capacity at constant pressure - . and T is temperature.TS Where H is the enthalpy. dG = dH .

TS dG = -SdT Substituting S gives an expression to determine the temperature dependence for the free energy d∆G dT = ∆G .Temperature dependence Starting from the definition of G.∆H T Gibbs-Helmholtz Equation Winter Corrosion For Engineers ENGR 4610 .10 - . G = H .

769 -393. graphite) + O2(g)  CO2(g) Often.∆H =F ∆ H°f .287 235. J/mol/K J/mol/K J/mol/K ∆ H°f .0 kJ/mol C(s.05 5.806 ENGR 4610 .501 220.11 Corrosion For Engineers - .68 205.806 235.063 12.18737. The Free Energy Function dT T -(G°T-H°298)/T and look up the basic thermodynamic values for the reactants 500K 700K 1000K and products.413 213.35 208.636 0 8.413 213.501 220.36 9. we want to know the thermodynamics of the reaction at temperatures other than room temperature.063 -(G°T-H°298)/T 12.363 213.298 500K 700K 1000K kJ/mol J/mol/K J/mol/K J/mol/K J/mol/K J/mol/K 0 1.298 kJ/mol 0 0 0 0 -393.14 -394.636 208.887 9.51 ∆ G°f .887 9.53 6.298 kJ/mol H°298-H°0 S°298 Cp.64 218. To do this.C(s.769 6.187 218.74 8. we use the Gibbs-Helmholtz relationship.287 225.03 29.11 225. graphite) O2 CO2 Winter d∆G = ∆G .

C(s. the value of the function (F) is given by: ∆Freac = ∆Ff(CO2) . graphite) + O2(g)  CO2(g) Once again.887 208.187 So.(6.12 - .413 218.887 J•mol-1•K-1 C(s. -(∆Gf° .413) 2.887 + 208.∆H298°)/T = F 218.(∆Ff(C) + ∆Ff(O2)) ELEMENT -(Gf°-H298°)/T / J•mol-1•K-1 500 K 6.187 . graphite) O2(g) CO2(g) Winter Corrosion For Engineers ENGR 4610 .

51 ∆ G°f .298 500K 700K 1000K kJ/mol J/mol/K J/mol/K J/mol/K J/mol/K J/mol/K 0 1.C(s.36 kJ•mol-1 Element ∆ H°f .5 J•mol-1 -394.03 29.(∆Hf(C) + ∆Hf(O2)) -(G°T-H°298)/T H°298-H°0 S°298 Cp. graphite) + O2(g)  CO2(g) -(∆Gr° .35 208.13 - .187 225.36 So: ∆Gr.769 9.806 -394.68 205.287 235.501 220.11 218.887 x 500 = -1443.0 kJ/mol C(s.∆H298°)/T = 2.887 9.95 kJ•mol-1 Winter Corrosion For Engineers ENGR 4610 .64 37.413 213.363 213.298 kJ/mol at 500K ∆Hreac = ∆Hf(CO2) .14 ∆ H°f .∆H298° = -2.74 8.298 kJ/mol 0 0 -393.05 5.063 12.500° = -1.53 6.636 0 8. graphite) O2 CO2 0 0 -393.887 J•mol-1•K-1 or: ∆Gr° .51 = -394.4435 + -393.

401 J/mol ∆ G° r. Temperature °C 24.85 K 298 500 700 1000 =Σ(( ∆ G° T-∆ H° 298 )/T) -(G° T-H° 298 )/T J/mol/K 2.723 2.91 Winter Corrosion For Engineers ENGR 4610 . graphite) + O2(g)  CO2(g) Summary These calculations can be repeated to determine the free energy at different temperatures.C(s.14 - .T kJ/mol -394.0 -395.42 2401.95 1906.5 -394.85 726.85 426.36 1443.887 2.85 226.1 -395.

∆H T Winter Corrosion For Engineers ENGR 4610 .15 - .d∆G dT = ∆G .

From A. Winter Corrosion For Engineers ENGR 4610 . An Introduction to Metallurgy.16 - . 1980.Ellingham diagrams Plot the free energy when one mole of gaseous oxygen at 1 atm pressure combines with a pure element to form oxide. Cottrell.

17 - .Winter Corrosion For Engineers ENGR 4610 .

G. Thermodynamics of Corrosion • Equilibrium constants • Basic thermodynamic relationships • H. S.18 - .Corrosion is the destructive attack of a metal by chemical or electrochemical reaction with its environment. Cp • Gibbs free energy • Free energy of formation Winter Corrosion For Engineers ENGR 4610 .

From A. Winter Corrosion For Engineers ENGR 4610 .19 - .Ellingham diagrams Plot the free energy when one mole of gaseous oxygen at 1 atm pressure combines with a pure element to form oxide. An Introduction to Metallurgy. Cottrell. 1980.

Free energy becomes more positive with increasing temperature Smaller driving force with increasing temperature Winter Corrosion For Engineers ENGR 4610 .Ellingham diagrams Free energy of formation for the metal oxides have positive slopes.20 - .

21 - Oxide Stable Metal Stable . the metal oxide will release oxygen and exist as a pure metal M + xO2 ← MO2x Winter Corrosion For Engineers ENGR 4610 .Ellingham diagrams M + xO2 → MO2x At a sufficiently high temperature.

22 - Oxide Stable Metal Stable .Ellingham diagrams M + xO2 → MO2x The lower the line. the more stable the oxide Kinks in the diagram indicate phase changes d∆G dT = -∆S Winter Corrosion For Engineers ENGR 4610 .

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