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 Titration is a laboratory method wherein the

concentration of a particular solute in a solution is


determined. In an acid-base titration, a solution with a
known concentration of base is slowly added to an acid
or vice versa. By monitoring the progress of the
reaction, a titration curve can be produced. A titration
curve is the graph of the pH as a function of the volume
of the added titrant. The equivalence point of a titration
curve is the point at which the quantities of an acid and
base that have been brought together are
stoichiometrically equivalent. The titration curve may be
used to determine the Ka of the weak acid or the Kb of
the weak base being titrated.
A. Preparation of Standard Titration Curves
 In a 100 mL beaker, 25 mL of 0.1 M HOAc was
measured and transferred. The initial pH was
determined with the use of a pH meter. The titrant,
0.1 M NaOH, was added by 1 mL increments. The
solution was stirred then the pH was recorded
afterwards. This was done after each addition of the
said titrant. After an abrupt change in the pH, the
volume of the increments added was changed to 0.5
mL. This was done until the pH was at 5-6 past
neutral.
 The procedure was repeated but with: (b) 0.1 M HCl as
initial solution and 0.1 M NaOH as the titrant and (c)
0.1 M NH4OH as the initial solution and 0.1 M HCl as
the titrant.
B. Analysis of Unknown
 The same procedure in Part A was done
but with 0.1 M HCl titrant used for the
unknown base and 0.1 M NaOH for the
unknown acid.
I. Titration of 25 ml 0.1 M HOAc, (which is a weak acid) and 0.1 M NaOH (which is a strong
base).

Before Titration: Initial pH of 0.1 M HOAc

HOAc + H2O H3O + + OAc-


Initial 0.1 M 0 0
Change -x +x +x
Equilibrium 0.1-x x x

Ka= [H3O + ] [OAc-] = 1.8 x 10 -5 (pH will depend on [H3O + ] = x)


[HOAc]
x2/ (0.1-x)= 1.8 x 10 -5
x= 1.3 x 10 -3 pH= -log (1.3 x 10 -3 ) = 2.89
Using the Henderson-Hasselbach equation, (pH= pKa + log
[base]/[acid]), it is possible to predict the change in pH as the
titrant is added.
 
+ 5 ml NaOH= 30 ml (solution) (before equivalence point)

0.1 M NaOH = 0.1 mol NaOH/ 1L= 0.1 mmol/ml


5 ml NaOH x 0.1 mmol/ml = 0.5 mmol
25 ml HOAc x 0.1 mmol/ml= 2.5 mmol
HOAc + OH- OAc- + H2O
Initial 2.5 mmol 0.5 mmol 0
Change -0.5 mmol -0.5 mmol +0.5 mmol

Equilibrium 2 mmol 0 0.5 mmol

pH= pKa + log ( [base]/[acid])

-log (1.8 x 10 -5 ) + log (2 mmol/30 ml)/ (0.5 mmol/30)


pH= 4.14
+ 25 ml NaOH= 50 ml (solution) (Equivalence point)
 
25 ml NaOH x 0.1 mmol/ml= 2.5 mmol

HOAc + OH- OAc- + H2O


Initial 2.5 mmol 2.5 mmol 0
Change -2.5 mmol -2.5 mmol +2.5 mmol

Equilibrium 0 0 2.5 mmol

OAc- (weak base) will undergo hydrolysis

OAc- + H2O HOAc + OH-

Assume [OH] is small and [NaOAc]= 2.5 mmol/50 ml= 0.05 M

Kb= [OH] [HOAc] / [OAc]= Kw/Ka= 1 x10 -14 / 1.8 x 10 -5 =5.6 x10 -10
Kw/Ka= 1 x10 -14 / 1.8 x 10 -5 = x2/ 0.05
x= 5.27 x 10 -6
pOH= -log (5.27 x 10 -6 ) pOH=5.28 pH= 14-5.28= 8.72
As 0.1 M NaOH is added in increments of 1 ml, the pH of the solution
shows little change because of the buffer solution being set up. Due
to its buffer capacity, which is the amount of acid or base (in this
case 0.1 M NaOH) the buffer can neutralize before the pH will
change to an appreciable degree. However, the change in pH
becomes more pronounced as it nears the equivalence point. The
pH of the solution depends on the concentration of HOAc that has
not been neutralized. The goal of titration is to reach the
equivalence point, which is the point where the added solute
(NaOH) reacts completely with the substance present (HOAc). In
this titration, equivalence point is attained when 25 ml of 0.1 M
NaOH is added to 25 ml of 0.1 M HOAc. Thus, the concentration of
the acid and base is the same. Since HOAc is a weak acid which
reacted to NaOH which is a strong base, the solution becomes
slightly basic at the equivalence point, with a pH of 8.72. The pH at
the equivalence point is always above 7 when a weak acid-strong
base titration happens, because the salt formed has an anion that
is a weak base (OAc-), which will undergo hydrolysis(pH upon
computation is 8.72). After the equivalence point, the pH is
determined by the concentration of OH- from the excess NaOH.
Theoretical Titration of 0.1 M Titration of 0.1 M HOAc with 0.1
HOAc with 0.1 M NaOH M NaOH

ml titrant pH
ml titrant pH ml titrant pH
0 2.89 0 3.11 20 5.32
1 3.4 21 5.43
5 4.14
2 3.67
22 5.58
10 4.56 3 3.85
23 5.77
4 3.98
15 4.92 24 6.09
5 4.09
20 5.34 6 4.2 25 6.63
7 4.3 26 9.88
25 8.72
8 4.37 26.5 10.22
30 11.96 9 4.45
27 10.82
10 4.52
35 12.22 27.5 10.93
11 4.6
28 11.21
40 12.36 12 4.67
13 4.73 28.5 11.32
45 12.46
14 4.81 29 11.39
50 12.52 15 4.88 29.5 11.46
16 4.95 30 11.52
55 12.57
17 5.03
30.5 11.57
60 12.61 18 5.11
31 11.6
19 5.22
II. Titration of 25 ml 0.1 M HCl (strong acid) with 0.1 M
NaOH (strong base)

Before Titration: Initial pH of 0.1 M HCl


[H+] = [HCl]
pH= -log (0.1M)
pH= 1

+ 5ml= 30 ml (solution)(before equivalence point)


Acid mmol= 0.1 mmol/ml x 25 ml= 2.5 mmol
Added Base mmol= 0.1 mmol/ml x 5 ml= 0.5 mmol
H3O + + OH- 2 H2O
Initial 2.5 mmol 0.5 mmol
Change -0.5 mmol -0.5 mmol

Equilibrium 2mmol 0

(pH will depend on [H3O + ])


pH= -log (2mmol/30 ml)
pH= 1.18
+ 25 ml= 50 ml (solution) (equivalence point)
Added base mmol= 0.1 mmol/ml x 25 ml= 2.5 mmol

H3O + + OH- 2 H2O


Initial 2.5 mmol 2.5 mmol
Change -2.5 mmol -2.5 mmol

Equilibrium 0 0

Since no excess acid or base is present, the solution is neutral.


pH=7

+30 ml= 55ml (solution) (after equivalence point)


Added base mmol= 0.1 mmole/ml x30 ml= 3 mmol

H3O + + OH- 2 H2O


Initial 2.5 mmol 3 mmol
Change -2.5 mmol -2.5 mmol

Equilibrium 0 0.5 mmol

(pH depends on excess [OH])


pOH= -log (0.5 mmol/55ml)
pOH= 2.04 pH= 14-2.04= 11.96
In a titration of a strong acid and a strong base, the
solution of the strong acid will always have a higher
initial pH (initial pH of HCl is 1, whereas initial pH of
HOAc is 2.89). Just as with HOAc, the initial pH
depends on the concentration of HCl. Before the
titration reaches the equivalence point, pH increases
slowly, but experiences a steeper rise of pH as it
reaches the equivalence point. Theoretically, in a
strong acid-strong base titration, the pH at the
equivalence point is always 7, because the cation of
the strong base (Na +) and the anion of the strong
acid (Cl-) do not hydrolyze. The pH of the solution
after the equivalence point will be determined by
the concentration of excess NaOH.
Theoretical Titration of 0.1 M HCl Titration of 0.1 M HCl with 0.1 M
with 0.1 M NaOH NaOH

ml titrant pH ml titrant pH ml titrant pH


1 1.67 21 1.95
0 1 22 2.01
2 1.63
5 1.18 23 2.12
3 1.59
24 2.24
10 1.37 4 1.57 25 2.45
5 1.58 26 2.92
15 1.6 6 1.67 27 6.36
7 1.63 27.5 9.67
20 1.95
8 1.62 28 10.38
25 7 28.5 10.77
9 1.61
29 10.91
30 11.96 10 1.62 29.5 11.07
11 1.64 30 11.22
35 12.22
12 1.65 30.5 11.29
40 12.36 13 1.67 31 11.33
31.5 11.4
14 1.69
45 12.46 32 11.43
15 1.71
32.5 11.46
50 12.52 16 1.74 33 11.51
55 12.57 17 1.77 33.5 11.51
18 1.8 34 11.52
60 12.61 34.5 11.56
19 1.84
35 11.57
20 1.9
35.5 11.59
Theoretical Titration of 0.1 M HCl w ith 0.1 M NaOH

14
12
10
8
pH
pH

6
4
2
0
0 20 40 60 80
ml NaOH
III. Titration of 25 ml 0.1 M NH4OH (weak base) with 0.1 M HCl (strong acid).

Before Titration: Initial pH of 0.1 M NH4OH


NH4OH + OH-
NH4 +

Initial 0.1 M 0 0
Change -x +x +x
Equilibrium 0.1-x x x

Kb= 1.8x 10 -5 = [NH4+] [OH-]/[NH4OH] Assume: 0.1 >>x


1.8x 10 -5 = x 2
X= 1.3 x 10 -3
pOH= -log (1.3 x 10 -3 ) = 2.89 pH= 14-2.89= 11.11
+ 5ml= 30 ml (solution) (before equivalence point)

Base mmol before titration= 0.1 mmol/ml x 25 ml= 2.5 mmol


Added acid mmol= 0.1mmol/ml x 5 ml= 0.5 mmol

NH4OH + H3O+ NH4 + + H2O


Initial 2.5 mmol 0.5 mmol 0

Change -0.5 mmol -0.5 mmol +0.5 mmol

Equilibrium 2 mmol 0 0.5 mmol

pOH=pKb + log [acid]/[base]


4.75 + log9.25 + log (0.5mmol/30 ml)/ (2mmol/30 ml)=4.15
pH= 14-4.15= 9.85
+25 ml= 50 ml (solution) (equivalence point)

Added acid mmol= 0.1 mmol/ml x 25= 2.5


mmoles
NH4OH + H3O+ NH4 + + H2O
Initial 2.5 mmol 2.5 mmol 0

Change -2.5 mmol -2.5 mmol +2.5 mmol

Equilibrium 0 0 2.5 mmol


Hydrolysis of NH4 +

NH4 + + H2O NH3 + H3O+


Initial 0.05 M 0 0
Change -x +x +x
Equilibrium 0 x x

Ka= [NH4OH] [H3O+] /[ NH4 +] =5.6 x 10 -10


5.7 x 10 -10 = [H3O+]2 /(2.5mmol/50 ml)
5.6 x 10 -10 = x2/0.05-x
x=5.29 x 10 -6
pH= -log (5.29 x 10 -6 )
pH= 5.27
+30 ml=55 ml (solution) (after equivalence point)

Added acid mmol= 0.1mmol/ml x 30 ml= 3 mmol

NH4OH + H3O+ NH4 + + H2O


Initial 2.5 mmol 3 mmol 0
Change -2.5 mmol -2.5 mmol +2.5 mmol

Equilibrium 0 0.5 mmol 2.5 mmol

pH= -log[H3O+]= -log (0.5 mmol/55ml)= 2.04


The pattern of the titration of a weak base-
strong acid is quite similar with the
titration of a weak acid-strong base,
except that the pH of the solution
decreases as the titration continues.
When titration reaches the equivalence
point, the cation of the weak base (NH4+)
will undergo hydrolysis, thus making the
pH less than 7 (upon calculation, pH at
equivalence point is 5.28). Similarly, the
pH after the equivalence point will depend
on the excess HCl present.
Theoretical Titration of 0.1 M Titration of 0.1 M NH4OH
NH4OH with 0.1 M HC with 0.1 M HC

ml titrant pH
ml titrant pH
0 9.9
0 11.11 1 9.64
2 9.49
5 9.85 3 9.28
4 9.12
10 9.43
5 8.98
15 9.07 6 8.78
7 8.56
20 8.65 8 8.26
9 7.75
25 5.28
10 5.73
30 2.04 10.5 3.08
11 2.66
35 1.78 11.5 2.48
12 2.36
40 1.64
12.5 2.28
45 1.54 13 2.21
13.5 2.16
50 1.48 14 2.11
14.5 2.07
55 1.43 15 2.04
60 1.39 15.5 2.01
16 1.98
Theoretical Titration of 0.1 M NH4OH w ith 0.1 M HCl Experimental Titration Curve of NH4OH w ith HCl

12 12
10 10
8 8
6 pH 6 pH
pH

pH
4 4
2 2
0 0
0 20 40 60 80 0 5 10 15 20
ml HCl ml HCl
Titration of Unknown with 0.1 M NaOH

Upon comparison with the theoretical titration curves, the unknown can be classified as
a weak acid, due to the less steep change in pH as compared to the theoretical
titration curve of a strong acid.
Concentration of unknown acid
[Concentration of NaOH] (Vol. NaOH)= [C. of unknown acid](Vol.at eq. point)
(0.1 M) (25 ml) = x [ (25 ml NaOH) + (27 ml unknown acid)]
x= 0.05 M
When comparing all the theoretical
titration curves with their respective
experimental values, there is little
difference in terms of the pattern the
plot follows. The difference is accounted
for by the different initial pH values
before titration as compared to the
theoretical pH values, which affects the
equivalence point during titration.
In these titration curves, determining the pH at each
step is essential. Before the titration reaches the
equivalence point, the pH of the solution depends
on the amount of the substance not yet neutralized
by the titrant. After reaching the equivalence point,
pH levels depend on the excess amount of the
titrant in the solution. Determining the pH at
equivalence point depends of the substances used
in titration. For a strong acid-strong base titration,
there is no need to compute for the pH level is
always seven, because no cations or anions
undergo hydrolysis, which will have an effect on its
pH level. If one of the components is a weak acid
or a weak base, the hydrolysis of the cation/anion
needs to be taken into account
Sources:

 Brown, Theodore L., Bursten, Bruce E.,


Lemay, H. Eugene Jr. (2000). Chemistry: The
Central Science. 8th ed.
 
 Silberberg, Martin S. (2007). Principles of
General Chemistry. McGraw-Hill Intl. ed.

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