Calculate the pH at each point listed for the titration of 50 mL of 0.

050 M formic acid (HCO2H, MW =

46.02, Ka = 1.80•10-4) with 0.050 M KOH. The points to calculate are Va = 0.0, 10.0, 25.0, 48.0,
50.0, 50.5, and 60.0 mL.
1. Determine the volume at equivalence point:
M Acid x V acid =M Base x V Base

M Acid x V acid
=V Base
M Base

0.050 M x 50 ml
=V Base
0.050 M

50 ml=V Base
2. pH of the solution before the addition of KOH @ 0.0 ml
The pH of the solution will be dependent on [H + ] of the solution.
Before Equivalence point

HCO2H + H20  HCO2- + H30+

Initial 0.050 M 0 0
Change -x +x +x
Equilibrium 0.050 M -x x x
ka=1.8x10-4

ka=¿ ¿ ¿

[x][ x]
1.8 x 10−4=
0.050−x

−4 2
1.8 x 10 [0.050−x ]=x

9.0 x 10−6−1.8 x 10−4 x=x 2

x 2+ 1.8 x 10−4 x−9.0 x 10−6=0

x=2.91 x 10−3
X= H30+
pH= -log(2.91 x 10−3 )
pH= 2.54

3. @ 50 ml of 0.050 M of HCO2H + 10 ml of 0.050 M of KOH

 Before Equivalence point

HCO2H + OH-  HCO2- + H20

Initial (0.050 M)(50ml) (0.050 M)(10 ml) 0 0
60 ml 60 ml
= 0.041667 = 0.00833

Change -0.00833 M 0.00833M +0.00833M +0.00833M

After complete .033337 M 0 0.00833 0.00833

neutralization
As concentration

HCO2H + H20  HCO2- + H30+

Initial . 033337 M 0.00833 0
Change -x +x +x
Equilibrium . 033337 M -x 0.00833 +x x

ka=¿ ¿ ¿

[ 0.00833+ x ] [x ]
1.8 x 10−4=
. 033337 M −x

1.8 x 10−4 [ . 033337 M −x ] =x 2 +0.00833 x

6.0 x 10−6−1.8 x 10−4 x=x 2+ 0.00833 x

x 2+ 8.51 x 10−3 x−6.0 x 10−6 =0

x=6.54687 x 10−4
X= H30+
pH=-log(H30+)
=-log(6.54687 x 10−4 ¿
pH=3.18

4. @ 50 ml of 0.050 M of HCO2H + 25 ml of 0.050 M of KOH

Before Equivalence point
 HCO2H + OH-  HCO2- + H20
Initial (0.050 M)(50ml) (0.050 M)(25 ml) 0 0
75 ml 75 ml
= 0.03333 M = 0.01667 M

Change -0.01666 M -0.01667 -0.01666 -0.01666

After complete 0.01666 M 0 0.01666M 0.01666M

neutralization
As concentration

HCO2H + H20  HCO2- + H30+

Initial . 0.01666 M 0.01666 0
Change -x +x +x
Equilibrium . 0.01666 -x 0.01666 + x x

ka=¿ ¿ ¿

[ 0.01666+ x ] [x ]
1.8 x 10−4=
0.01666−x

1.8 x 10−4 [ 0.01666−x ] =x 2+ 0.01666 x

2.99 x 10−6−1.8 x 10−4 x =x2 +0.01666 x

x 2+ 0.01684 x−2.99 x 10−6=0

x=1.75719 x 10−4
X= H30+
pH=-log(H30+)
=-log(6.54687 x 10−4 ¿
pH=3.75

5. @ 50 ml of 0.050 M of HCO2H + 48 ml of 0.050 M of KOH

Before Equivalence point
 HCO2H + OH-  HCO2- + H20
Initial (0.050 M)(50ml) (0.050 M)(48 ml) 0 0
98 ml 98 ml
= 0.02551 M = 0.02449 M

Change -0.02449 M -0.02449 M -0.02449 M -0.02449 M

After complete 0.00102M 0 0.02449 M 0.02449 M

neutralization
As concentration

HCO2H + H20  HCO2- + H30+

Initial 0.00102M 0.02449 M 0
Change -x +x +x
Equilibrium . 0.00102-x 0.02449 M + x x

ka=¿ ¿ ¿

[ 0.02449+ x ] [x ]
1.8 x 10−4=
0.00102−x

1.8 x 10−4 [ 0.00102−x ] =x2 +0.02449 x

1.84 x 10−7−1.8 x 10−4 x=x 2+ 0.02449 x

x 2+ 0.02467 x−1.84 x 10−7=0

x=7.4562 x 10−6
X= H30+
pH=-log(H30+)
=-log(7.4562 x 10−6 ¿
pH=5.13

6. @ 50 ml of 0.050 M of HCO2H + 50 ml of 0.050 M of KOH

Equivalence point

HCO2H + OH-  HCO2- + H20

 Initial (0.050 M)(50ml) (0.050 M)(50 ml) 0 0
100 ml 100 ml
= 0.025 M = 0.025 M

Change -0.025 M -0.025 M -0.025 M -0.025 M

After complete 0 0 0.025 M 0.025 M

neutralization
As concentration

Hydrolysis
HCO2- + H20  HCO2H + OH-
Initial 0.025M 0 0
Change -x +x +x
Equilibrium . 0.025-x +x x

1.0 x 10−14
kb= =[HC 02 H ]¿ ¿
1.8 x 10−4

[ x ] [x ]
5.56 X 10−11 =
0.025−x

X is negligible
[ x ] [ x]
5.56 X 10−11 =
0.025

[5.56 X 10 ¿¿−11][0.025]=x 2 ¿

1.39 X 10−12=x 2

x=1.789 x 10−6
X= OH-
pOH=-log(OH-)
=-log(1.789 x 10−6
p0H=5.93
pH=8.07

After equivalence point

At 50.5 mL: pH determined by excess NaOH present

[OH-] = (excess volume/total volume)(M)
(0.5/100.5)(0.050) = 2.49•10-4 M → pH = 10.40

At 60.0 mL: pH determined by excess NaOH present

[OH-] =(excess volume/total volume)(M)
(10.0/110)(0.050) = 4.55•10-3 M → pH = 11.66