Chemistry 122, Dr.

Haug; Quiz #8

Name _____KEY_________________

(1) (10 pts) Consider the titration of the following buffer solution: the 40.00mL buffer solution is
characterized as 0.200M NH3 and 0.250M NH4Cl.
(a) Calculate the pH of the pure buffer solution. KbNH3 = 1.8x10-5 so KaNH4+ = Kw/ KbNH3 = 5.6x10-10
(i) Notice that this is a buffer and just use the H-H Eq for the buffer situation:
pH = 9.26 + log ( [0.20] / [0.25] ) = 9.16
where pKa = -log (5.6x10-10 ) = 9.26
(ii) Or carry out the reaction table method with the base reaction (the logical approach based
on the chemistry, i.e. compare the K values and you expect a basic solution):
NH3(aq) + H2O OH-(aq) + NH4+(aq)
(M units)
NH3 OH NH4+
I
0.20 0?
0.25
change
-x
+x
+x
E
0.20-x x
0.25 + x
.
Kb = (0.25 +x ) ( x ) / (0.20 x) (0.25) x / (0.20) = 1.8x10-5
x= 1.44x10-5 and pOH = 4.84 so pH = 9.16 (same as with H-H method)
YOU DO NOT NEED TO DO IT BOTH WAYS Just the HH equation is fine!
(b) Calculate the solution pH when 4.00mL of 1.00M HCl has been added to the buffer solution.
The neutralization reaction proceeds far to the right (i.e. to completion):
H+(aq) + NH3 (aq) NH4+ (aq)
K = 1 / 5.55x10-10 = 1.8x10+9
(mmol units)
I
Add H+
Neut Rxn
NewI

H+
0?
+4.00
-4.00 -4.00
4.00
0?
NH3
8.00

NH4+
10.00
+4.00
14.00

Clearly in the range of HH, so the H-H Eq is:

pH = pKa + log ( [CB] / [WA] )
pH = 9.26 + log ( [4.00/44.00] / [14.00/44.00] ) = 9.26 + log(4/14) = 8.71

(c) Calculate the solution pH when 8.00mL of 1.00M HCl has been added to the buffer solution.
The neutralization reaction proceeds far to the right (i.e. to completion):
H+(aq) + NH3 (aq) NH4+ (aq)
K = 1 / 5.55x10-10 = 1.8x10+9
(mmol units) NH3
H+
NH4+
I
8.00 0?
10.00
+
Add H
+8.00
Neut Rxn
-8.00 -8.00
+8.00
NewI
0.00
0?
18.00
.
This is the H+:NH3 equivalence point: (40.00mL)x(0.200M)=8.00mmol = (8.00 mL)x(1.00M)
Results in [NH4+] = (18.00) mmol NH4+ / (40.00+8.00)mL = 0.375M
The remaining reaction is then the dissociation of this weak acid:
NH4+ (aq) H+(aq) + NH3 (aq)
(M units)
NH4+
H+
NH3
I
0.375
0?
0
change
-x
+x
+x
E
0.375-x
x
+x
.
Ka = ( x ) ( x ) / (0.375 x) x2 / (0.375) = 5.55x10-10
x= 1.44x10-5 and pH = - log(x) = 4.84
(d) Calculate the pH of the solution when 10.00mL of 1.00M HCl has been added to the buffer solution.
We used 8.00mL to reach the equivalence point. Now we have 2.00mL of strong acid HCl
( 2.00 mmol of H+ ) beyond the equivalence point:
[H+] = (2.00) mmol / (40.00+10.00)mL = (2.00/50.00)M = 0.0400M
pH = - log(0.0400) = 1.40
i.e. The added strong acid totally trumps the acidity of the Ammonium Ion weak acid, which we used
in part (c), so we safely ignore it in part (d). Or, if you do not believe this, then:
NH4+ (aq) H+(aq) + NH3 (aq)
(M units)
NH4+
H+
NH3
I
0.375
0.04
0
change
-x
+x
+x
E
0.375-x
0.04+x
+x
.
Ka = ( x ) ( 0.04+x ) / (0.375 x) x (0.04) / (0.375) = 5.55x10-10
x= 2.08x10-8 so x << 0.04 and therefore [H+] = 0.040M and so pH = 1.40
(e) Calculate the solution pH when 4.00mL of 1.00M NaOH has been added to the original buffer solution.
Recall: 40.00mL buffer solution is characterized as 0.200M NH3 and 0.250M NH4Cl. KbNH3 = 1.8x10-5
The neutralization reaction proceeds quite far to the right:
NH4+ (aq) + OH-(aq) NH3(aq) + H2O K = Ka/Kw = 5.5x10+4
(mmol units) NH4+ OHNH3
I
10.00 0?
8.00
Add OH+4.00
Neut Rxn
-4.00 -4.00
+4.00
NewI
6.00
0?
12.00
.
This is in the range of H-H Eq so this gives:
pH = pKa + log ( [CB] / [WA] )
pH = 9.26 + log ( [12.00/44.00] / [6.00/44.00] ) = 9.26 + log(12/6) = 9.56
2