1

ACID/BASE TITRATION
EXPERIMENT 2


INTRODUCTION
In PART I of this experiment, you will determine the concentration (molarity) of a sodium
hydroxide solution (NaOH) by titrating an acid, the potassium biphthalate (HOOCC
6
H
4
COOK).
The equivalence point will be determined by the change in color of the Phenolphthalein indicator.
Knowing that one mole of NaOH neutralizes one mole of HOOCC
6
H
4
COOK, the molarity of the
sodium hydroxide solution can be determined from the volume of base added to reach the
equivalence point, and the weigh of biphthalate acid used. The accurate determination of the NaOH
solution molarity is called standardization. After PART I, the NaOH solution will be called
Standard NaOH solution.
In PART II of this experiment, you will determine the molarity of an unknown weak acid by a pH-
titration with your own Standard NaOH solution. Measuring the pH of the solution and the volume
of NaOH added as the titration proceeds, a titration curve (graph) will be constructed. The
equivalence point, the pK
a
and K
a
of the unknown acid can then be determined from the curve.
Mastering the techniques when using the pipet, buret and analytical balance will be crucial here.


THEORY
Acid/base titration is the process of mixing measured volumes of acid and base solutions in such a
manner that you can determine when, equivalent amounts (moles) of each are present. The purpose
of titration is to determine the concentration of one solution (the base in PART I of this
experiment), while the concentration of the other (the acid) is known to a high degree of accuracy.
The reaction of an acid HA with a base B is called neutralization, and is represented by equation
(1).
HA + B A

+ BH
+
(1)
An acid/base neutralization reaction is simply a proton (H
+
) transfer. The acid acts as a proton
donor, the base as a proton acceptor.
The equivalence point of a titration is the point at which equivalent amounts (number of moles) of
acid and base have been mixed. In order to determine the equivalence point, a visual indicator is
added to the solution to be titrated. When properly selected, the indicator undergoes a sharp color
change slightly after the equivalence point. So slightly in fact that we consider the color change to
happen precisely at the equivalence point.
2
In PART I of this experiment, a precisely known (weighed) amount of acid HA is placed into an
erlenmeyer flask, along with a few drops of indicator HInd, water, and a magnetic stir bar. The flask
is then set under a buret, as shown in Figure 1. The buret is filled with base B solution. While the
base is slowly added to the erlenmeyer flask, reaction (1) occurs as long as HA is present in the
flask. When the last molecules of acid HA have reacted, the next drop of base B will react with the
indicator as shown by reaction (2), and the solution will turn pink.
HInd + B Ind

+ BH
+
(2)

Colorless pink
Reaction (2) is a neutralization reaction where base B reacts with the acid HInd. To be appropriate,
the indicator must have the following characteristics:
- the acid form HInd must be of a different color than the basic form Ind

,
- potent dye,
- HInd must be a weaker acid than the titrated acid HA.

Figure 1 Titration setup when using a color indicator.

In order to understand better the idea behind pH-titration (PART II), we will now focus on the
chemical species present in the solution during a titration, and their impact on the pH. In the
titration of a weak acid HA, the system (in the solution) is determined by the partial dissociation of
HA
HA + H
2
O

H
3
O
+
+ A

(K
c
= K
a
) (3)
and by
A

+

H
2
O

HA + OH

(4)


3
Before the titration starts, the solution contains HA and H
2
O, the system at that point is completely
determined by equilibrium (3).

When the titration begins, the base added (OH

) reacts with the acid HA according to the

neutralization reaction,
HA + OH

H
2
O + A

(5)
which is not an equilibrium but a complete forward reaction. The neutralization will obviously
decrease the amount of HA in the solution, and increase the amount of A

. As more base is added,

HA transforms into A

and equilibrium (4) becomes more important.

When half the initial amount of HA has been neutralized, the amount of HA and A

in the solution
are equal, and equilibria (3) and (4) are equally important. At that point, K
a
= [H
3
O
+
]. This is what
we call half-volume condition.

The equivalence point is reached when enough base has been added to react all the HA initially
present, leaving only A

and H
2
O in the solution. The system at this point is completely determined
by equilibrium (4). The pH of the solution is therefore slightly basic. Figure 2 shows how the pH
typically changes during a titration.

Past the equivalence point, the excess OH

added remain in solution, shifting equilibrium (4) to the

left, increasing drastically the pH of the solution.

20 15 10 5 0
0
1
2
3
4
5
6
7
8
9
10
11
12
13
14
NaOH added (mL)
pH

Figure 2 Titration curve of a weak acid with NaOH

4
APPARATUS AND CHEMICALS
3 125 mL erlenmeyer 1 100 mL grad. cylinder NaOH solution
1 500 mL erlenmeyer 1 10 mL grad. cylinder Unknown weak acid solution
3 50 mL beaker 1 magnetic stir plate + bar Potassium biphthalate 99.5%
1 150 mL beaker 1 pH electrode + interface Phenolphthalein solution
1 10.00 mL pipet + bulb acetone
1 25.00 mL buret distilled water


PROCEDURE
PART I Standardization of the NaOH solution.
Preparation of the NaOH solution. Obtain 10 mL of the stock NaOH solution directly into a
500mL erlenmeyer flask. Using a 100mL graduated cylinder, add 190mL of distilled water to
the same erlenmeyer (this will dilute the stock NaOH by a factor of ~20). Cap the flask and swirl
for a few seconds. Handle that solution with great care from then on.
Standardization. Rinse your buret three times with about 5 mL of your NaOH solution. Fill
the buret to near the 0.00 mL mark with the same solution. Make sure the tip of the buret is filled
and contains no air. Install the buret and stir plate as shown in Figure 1.
Precisely weigh approximately 0.18g of potassium biphthalate directly into a clean and dry 125
erlenmeyer flask. Add about 50 mL of distilled water, 4 drops of Phenolphthalein, and a stir bar.
Put the flask on the stir plate and set a gentle stir. Titrate until a faint pink color persists for at
least 30 seconds. Perform at least three of these titrations. Record all measurements in Table 1.
PART II Titration of the unknown weak acid.
Prepare the computer for data collection by opening the file Experiment 24a from the folder
Chemistry with Vernier. The vertical axis has pH scaled from 0 to 14 pH units. The horizontal axis
has volume scaled from 0 to 25 mL.
Calibration of the pH sensor
First Calibration Point
- Choose Calibrate from the Experiment menu and then click
Perform Now
.
- For the first calibration point, rinse the pH sensor with distilled water, then place it into a
buffer of pH=4.00.
- Type 4 in the edit box as the pH value.
- Swirl the sensor, wait until the displayed voltage for Input 1 stabilizes, click
Keep
.
Second Calibration Point
- Rinse the pH sensor with distilled water, and place it into a buffer of pH=7.00.
- Type 7 in the edit box as the pH value for the second calibration point.
- Swirl the sensor and wait until the displayed voltage for Input 1 stabilizes. Click
Keep
,
then click
OK
.
5
Titration of the unknown acid
1. Pipet 10.00 mL of the unknown acid solution into a 150-mL beaker. Add 50 mL of distilled
water, or just enough to soak the pH electrode properly.
2. Place the beaker on a magnetic stirrer and add a stirring bar.

Figure 3 Titration setup for pH-titration.
3. Use a utility clamp to suspend a pH Sensor on a ring stand as shown in Figure 3. Place the pH
Sensor in the solution and adjust its position so that it is not struck by the stirring bar.
4. Fill the buret with your standard NaOH solution. Make sure to adjust at the 0.00-mL level of
the buret.
5. Before adding NaOH titrant, click
Collect
and monitor pH for 5-10 seconds. Check that the
Meter window shows an acidic pH value. Once the displayed pH reading has stabilized, click
Keep
. In the edit box, type 0 (for 0 mL added). Press the ENTER key to store the first data
pair for this titration.
6. You are now ready to begin the titration.
a) Add the next increment of NaOH titrant (enough to raise the pH about 0.15 units). Let the
pH stabilizes for 5 seconds, then click
Keep
. In the edit box, type the current buret reading,
to the nearest 0.01 mL. Press ENTER. You have now saved the second data pair.
b) Continue adding NaOH solution in increments of ~1 mL, or, enough to raise the pH by
about 0.15 units, whatever comes first. Enter the buret reading after each increment.
c) Stop when 25mL of NaOH solution have been added.

7. When you have finished collecting data, click
Stop
. Dispose of the beaker contents to the
sink.
6

Warning !
Proceeding further when data collection has not been stopped,
may end up in permanent loss of all collected data.
8. To print a copy of the Table: click on the frame of the Table Window, then choose Print Window
from the File menu, enter your name(s) and click OK. Enter the number of copies and click OK.
9. To print a copy of the Graph: click on the frame of the Graph Window, then choose Print Window
from the File menu, enter your name(s) and click OK. Enter the number of copies and click OK.
10. The equivalence-point is located exactly at the inflexion point of the titration curve. To
determine its position, examine the graph of the first derivative (ApH/AVol) vs Volume. Click
the pH vertical-axis label of the graph, check the box for first derivative, uncheck the pH box,
then click OK. Reset the y axis by clicking on any y axis number and then select Autoscale.
Then print the Graph Window (step 9). Indicate with a mark (use a pen), the position of the
equivalence point on the titration curve.

At the end of the lab period:
- the pH electrode must be rinsed thoroughly with distilled water and returned to the storing
jar.
- the buret must be rinsed three times with distilled water, and left upside down on the stand
with the valve open.
7
CALCULATIONS
The key relation to determine the molarity of your NaOH solution is:
M
A
V
A
= M
B
V
B
(6)
where: M
B
: molarity of the NaOH solution
V
B
: volume of NaOH used to get to the equivalence point
M
A
: molarity of the biphthalate solution
V
A
: volume of the biphthalate solution used

In fact, equation (6) is simply another way to express the meaning of the equivalence point, where

n
A
= n
B
(

n
A
: number of moles of biphthalate acid, n
B
: number of moles of NaOH)

To calculate M
B
in PART I, you will therefore use equation (7):
n
A
= M
B
V
B
(7)
Knowing the molecular weight of potassium biphthalate (MW=204.23g/mol), n
A
can be calculated
from the weights in Table 1.
Determine the molarity of your unknown acid solution. First calculate the number of moles of
NaOH required to titrate the sample to the equivalence point (determined from the titration curve).
Then use the volume of acid sample to calculate the molarity of the acid.
As explained earlier, the pK
a
of your acid is calculated from the titration half-point, where the
number of moles of base added is equal to half the number of moles of total acid. Since at this
point, half of the original HA has been converted (to a very good approximation) to A

, we have
[A

] ~ [HA] or [A

]
[HA]
Therefore, this half-volume condition is a special situation where


K
a
=
[ H
3
O
+
] [ A

]
[ HA ]
= [ H
3
O
+
]
(9)
Taking the negative log of each side we obtain:
pK
a
= pH (10)


~ 1 (8)
8

Precision
The term precision describes the reproducibility of results. It can be defined as the agreement
between multiple measurements that have been made under the same conditions. The precision of a
set of measurements is related to the deviation of the data set from the average.
Trial # Data
Deviation
from average

1 0.315 0.004 = ABS(0.319 0.315)
2 0.321 0.002 = ABS(0.319 0.321)
3 0.320 0.001 = ABS(0.319 0.320)
average 0.319 0.002

So the average is 0.319 with an average deviation of 0.002.
Or, in terms of percent average deviation (precision or relative deviation)
Percent Average Deviation =
average
iation averagedev
x 100% =
319 . 0
002 . 0
x 100% = 0.6%

All deviation values (average and percent) must be reported with ONE significant figure only.
9

ACID/BASE TITRATION
Experiment 2 Data
Name


First Last ID
Demonstrator

Section

Lab Date


Table 1 Titration of weighed amounts of potassium biphthalate
Trial Mass of biphthalate Volume of NaOH sln
Initial Final added
# (g) (mL) (mL) (mL)
1

2

3

4

5

6


Table 2 pH-titration of the unknown acid solution
Code number of unknown acid
Initial volume reading of NaOH solution in the buret


Before handing in this Data Sheet, please attach (staple):
1. Titration curve
2. First derivative curve
3. Data Table (from computer)
Data sheet, hand in before leaving the lab
10

ACID/BASE TITRATION
Experiment 2 Lab report
Name


First Last ID
Demonstrator

Section

Lab Date



Table 3 NaOH molarity from titration of weighed amounts of potassium biphthalate
Trial

m
A
* n
A
V
B
M
B
Deviation from
M
B
average
# (g) (mol) (L) (mol/L) (mol/L)












*m
A
: mass of potassium
biphthalate from Table 1
Average

Percent deviation



Table 4 Concentration and strength of the unknown acid. (Code of unknown acid: _______)
M
B

V
B
V
A
M
A
K
a
pK
a

(mol/L) (L) (L) (mol/L) (mol/L)

M
B
from Table 3 (average)
Lab report, hand in within 24 hours
11

QUESTIONS
1. Show all the steps and calculations involved to complete the first row of Table 3 and 4.


























2. Why is it important that the indicator be a potent dye ? Explain.

Lab report, hand in within 24 hours

12

3. At the beginning of a titration to standardize the NaOH solution, Student A adjusted very
carefully the initial burette volume to 0.00mL. But he did not notice an important air bubble in
the tip of the burette. At the end of the titration, the air bubble is gone. Explain the effect of
that mistake on the calculated molarity M
B
. (Will the experimental M
B
calculated by Student A
be higher or lower than the true M
B
value?)

Lab report, hand in within 24 hours

13
Questions and problems

1. What indicator is used in this experiment?
2. What is the chemical formula of the acid used to standardize the NaOH solution ?
3. During standardization, whats the color of the solution in the erlenmeyer flask at the
equivalence point ?
4. Define equivalence point.
5. Write the equation for the reaction of NaOH with the indicator. (Use Hind as the chemical
formula of the indicator).
6. You used 15.44 mL of NaOH(0.1022M) to neutralize 10.00 mL of HA solution. Knowing that
K
a
(HA)=2.010
5
and K
b
(A

)=5.010
10
, answer the following questions:
a) Write down the chemical equation for the neutralisation of HA by NaOH.
b) Calculate the pH at the beginning of the titration, before adding any NaOH




Answers
1. Phenolphthalein
2. HOOCC
6
H
4
COOK
3. Pink (its possible that the pink color fades away 30 seconds after equivalence has been
reached)
4. The equivalence point of a titration is the point at which equivalent amounts (number of
moles) of acid and base have been mixed.
5. HInd + NaOH NaInd + H
2
O or HInd + OH

Ind

+ H
2
O.

6a. HA + OH

H
2
O + A

6b. M
A
= M
B
V
B
/ V
A
= 0.102215.44 / 10.00 = 0.1578 M
[HA] = 0.1578 M
HA + H
2
O A

+ H
3
O
+
0.1578 --- 0 10
-7
-x -x +x +x
0.1578-x --- x x+10
-7
x <<0.1578
x >>10
-7
x
2
/0.1578 = 2.010
5
x = 1.810
3
pH = Log(1.810
3
) = 2.8