Graphical Solutions:

Caution regarding drawing weak

bases
Example: 10-2M Ammonia solution
Let us find the equilibrium pH and all specie concentrations of a
solution of the weak base, ammonia, using graphical solution
technique.
The charge balance and proton condition are identical for this system
 56'( [86 ) ]
Now be careful! 𝐾𝑏 =
[56* ]

• Remember that we developed the plotting equations using pH as the master

variable. That is, pH is in the x-axis.
• However, when take a look at Kb equation, there is no pH but pOH!
• So, here we need to make a decision, we either devise new plotting equations
for [NH3] and [NH4+] using pOH as the master variable (but this would mean,
the plotting equations for [H+] and [OH-] would also need to be changed!)
OR
• We draw the graph using our usual, good old, pC-pH by just converting pKb
into pKa!
à pKw = pKa + pKb
𝐾% = 𝐾& ×𝐾'

𝐾% = 𝐻( [𝑂𝐻) ]

( ) * ( [,* )]
𝐻 [𝑂𝐻 ] = 𝐾& ×𝐾' 𝐾& = .+

/*'( [,* )]
So for the ammonia system, when 𝐾𝑏 =
[/**]

[/**]
Then 𝐾& = 𝐻( 𝑂𝐻) .
/*'( [,* )]
So this is what we are going to
* ( [/**] plot for the ammonia system
Or simply, 𝐾& = on the pC-pH diagram!
/*'(
In other words…
• When we have a base solution, and we are going to use the
graphical solution
• We will not put pKb on the graph!!, but we will convert pKb into
pKa using the relationship:
𝐾: = 𝐾; ×𝐾<
• & then plot the system.
• Here, we need to be careful where the base will dominate and
where the conjugate acid will dominate.
• As before, base will dominate in the basic region (i.e. right hand
side of the pH=pKa line) and the conjugate acid will dominate in
the acidic region (i.e. left hand side of the pH=pKa line)
Let’s find the [H+] + [NH4+] [OH-]
equilibrium point [OH-]

[NH4+] [NH3]
• We will find the point on
the graph that satisfies
the proton condition or
the charge balance

LOG (SPECIES)
(they are identical).
𝑵𝑯>
𝟒 ] + [𝑯
>
= [𝑶𝑯? ]

• pH at equilibrium =10.6
• 𝑁𝐻=> = 10?@.@ 𝑀
• 𝑂𝐻 ? = 10?@.@ 𝑀
• [NH3] = 10?B 𝑀 0 1 2 3 4 5 6 7 8 9 10 11 12 13 14
pHeq = 10.6
pH pKa
One last time…
• If you have a base added into water & you are going to solve the
system using a pC-pH diagram
• MAKE SURE TO CONVERT the Kb value into Ka and plot the system
accordingly!
• DO NOT put the value of pKb and plot a pC-pH diagram, IT WOULD
BE COMPLETELY WRONG!