Exercises (review)
Find the condition (pH) under which Mn(OH)2 precipitates when sodium hydroxide is added to seawater when processing samples by the Winkler method.
【Original form】 【Product form】
Mn(OH)2 ⇆ Mn2+
+ 2OH-
Gf0 (kJ/mol) -615.4 -228 -157.2×2
The total difference in standard Gibbs energy of formation for this reaction is, ⊿∑Gf0 = ΣGf0【Product form】-ΣGf0【Original form】 = 73×103
( J/mol )
Substitute a numerical value into the conditional equation for chemical equilibrium (ΔGf0 = -R・T・lnK).
73×103 ( J/mol ) = -8.314・298.15・ln(【Mn2+ mol/L】・【OH- mol/L】2/【Solid activity (=1) 】)
ln【Mn2+】・【OH-】2 = -29.45 , then 【Mn2+】・【OH-】2 = e-29.45 = 1.6×10-13.
If the pH of seawater is 8,
【OH-】= 10-6 mol/L, so 【Mn2+】= 1.6・10-1
mol/L
If we set alkaline pH 10,
【OH-】= 10-4 mol/L, so 【Mn2+】= 1.6・10-5
mol/L
If pH 12 is set,
【OH-】= 10-2
mol/L, so 【Mn2+】= 1.6・10-9 mol/L (Almost insoluble. Precipitates as manganese hydroxide)////////////////////////////////////////////////////////////////////////////////////////////////////