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A saturated solution of H_2S in water has concetration of approximately 0.10 M. What is the pH of this soluton and equilibrium concentrations of H_2S,HS^(-) andS^(2-)? Hydrogen sulphide is a diprotic acid and its dissociation constants are K_(a_1)=9.1xx10^(-8) ,K_(a_2)=1.3xx10^(-3) "mol L"^(-1) respectively.

Answer»


Solution :The SECOND dissociation CONSTANT is very very small than first dissociationconstant and therefore , the concentration of `H_3O^+` is obtained only from the first dissociation :
`{:(,H_2S+H_2O hArr, H_3O^(+)+, HS^-),("Initial conc.", 0.10,0,0),("At equilibrium" , 0.10-x, x ,x):}`
(x is amount of `H_2S` dissociated )
`K_(a_1)=([H_3O^+][HS^-])/([H_2S])=9.1xx10^(-8)`
or `(x xx x)/(0.10-x)=9.1xx10^(-8)`
Solving `x=9.5x10^(-5)`
`therefore [H_3O^+]=[HS^-]=9.5xx10^(-5) "mol L"^(-1)`
`pH=-log [H_3O^+]=-log (9.5xx10^(-5))`
`=-log 9.5 +5 =-0.98+5=4.02`
`[H_2S]=0.10-9.5xx10^(-5)`=0.10 M
To calculate the concentration of `S^(2-)` ion , we are to consider the second dissociation :
`{:(,HS^(-)+H_2O hArr, H_3O^(+)+,S^(2-)),("Initial conc.", 9.5xx10^(-5), 9.5xx10^(-5),0),("At equi.",9.5xx10^(-5)-x, 9.5xx10^(-5)+x ,x):}`
`K_(a_2)=([H_3O^+][S^(2-)])/([HS^-])`
`=((9.5xx10^(-5)+x)xx x)/(9.5xx10^(-5)-x)`
Assuming x to be very very small :
`9.5xx10^(-5)-x APPROX 9.5 xx10^(-5)` and `9.5xx10^(-5)+x`
=`9.5xx10^(-5)`
Solving `x=1.3xx10^(-13)`
`therefore [S^(2-)]=1.3xx10^(-13)`
Thus, `[H_3O^+]=9.5xx10^(-5)` M , `[HS^-]=9.5xx10^(-5)` M, `[S^(2-)]=1.3xx10^(-13)M , [H_2S]`=0.01 M , pH=4.02


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