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47 PHYWE Systeme GmbH & Co.

KG D-37070 Gttingen Laboratory Experiments Chemistry


Dissociation equilibrium 03.09
LEC 03 Chemical equilibrium
Principle and tasks
Carboxylic acids are potential elec-
trolytes, which exist in a weakly
dissociated condition in aqueous
solutions. The location of the disso-
ciation equilibrium is quantitatively
described by the K
a
or pK
a
value,
which can be determined with po-
tentiometric measurements.
Neutralisation curve of formic acid.
True and potential electrolytes
Strong and weak acids
Law of mass action
Henderson-Hasselbalch
equation
Dissociation constant and
pK
a
value
Substituent effects
Potentiometry
Set automatic titration with Cobra3 Chem-Unit 43040.88 1
Storage flask for pH-electrodes 18481.20 1
Immersion probe NiCr-Ni, Teflon, 300C 13615.05 1
Motor piston burette, 50 ml 36499.93 1
Rubber stopper, d = 18/14 mm, 1 hole 39254.01 1
Magnetic stirrer, mini 47334.93 1
Magnetic stirrer bar, l = 15 mm 46299.01 1
Glass beaker, 50 ml, tall 36001.00 2
Glass beaker, 150 ml, tall 36003.00 1
Precision balance CPA 623S (620 g/ 0.001 g),
set with software 49224.88 1
Volumetric flask, 100 ml 36548.00 6
Volumetric pipette, 5 ml 36577.00 6
Pipettor 36592.00 1
Pipette dish 36589.00 1
Pasteur pipettes 36590.00 1
Rubber bulbs 39275.03 1
Microspoon 33393.00 1
Wash bottle, 500 ml 33931.00 1
Buffer solution, pH 4.62, 1000 ml 30280.70 1
Buffer solution, pH 9.00, 1000 ml 30289.70 1
Formic acid acid 98...100%, 250 ml 30021.25 1
Acetic acid 99100%, pure, 1l 31301.70 1
Monochloracetic acid, 100 g 30060.10 1
Propionic acid, 500 ml 31753.50 1
N-butyric acid, 100 ml 30047.10 1
Lactic acid, 100 ml 30264.10 1
Caustic soda solution, 0.1 M, 1000 ml 48328.70 1
Water, distilled, 5 l 31246.81 1
PC, Windows XP or higher
What you need:
What you can learn about
Dissociation equilibrium P3030940
Related concepts
True and potential electrolytes, strong and weak acids, law of
mass action, Henderson-Hasselbalch equation, dissociation
constant and pK
a
value, substituent effects, potentiometry.
Principle
Carboxylic acids are potential electrolytes which exist in a weak-
ly dissociated condition in aqueous solutions. The location of the
dissociation equilibrium is quantitatively described by the K
a
or
pK
a
value which can be determined with potentiometric mea-
surements.
Tasks
Measure the alteration of the pH value during a titration of
approximately 0.1 molar aqueous solutions of formic acid, acetic
acid, monochloroacetic acid, propionic acid, butyric acid and
lactic acid with a 0.1 molar sodium hydroxide solution at con-
stant temperature using the Cobra3 system. From the neutrali-
sation curves read the pK
a
values of the acids and compare
them.
Equipment
Set automatic titration with Cobra3 Chem-Unit 43040.88 1
Storage flask for pH electrodes,
filled with 3.0 M KCl solution 18481.20 1
Glass beaker, 50 ml, tall 36001.00 2
Glass beaker, 150 ml, tall 36003.00 1
Set of precision balance Sartorius CPA623S
and measure software 49224.88 1
Volumetric flask, 100 ml 36548.00 6
Volumetric pipette, 5 ml 36577.00 6
Pipettor 36592.00 1
Pipette dish 36589.00 1
Pasteur pipettes 36590.00 1
Rubber bulbs 39275.03 1
Microspoon 33393.00 1
Wash bottle, 500 ml 33931.00 1
Buffer solution, pH 4.62, 1000 ml 30280.70 1
Buffer solution, pH 9.00, 1000 ml 30289.70 1
Formic acid acid 98...100%, 250 ml 30021.25 1
Acetic acid 99...100%, pure, 1000 ml 31301.70 1
Monochloracetic acid, 100 g 30060.10 1
Propionic acid, 500 ml 31753.50 1
N-butyric acid, 100 ml 30047.10 1
Lactic acid, 100 ml 30264.10 1
Caustic soda solution, 0.1 M, 1000 ml 48328.70 1
Water, distilled, 5 l 31246.81 1
PC, Windows

95 or higher
PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3030940 1
LEC
03.09
Dissociation equilibrium
Fig. 1. Experimental set-up.
Set-up and Procedure
Set up the experiment as shown in Fig. 1.
Prepare approximately 0.1 molar solutions of each of the car-
boxylic acids which are to be investigated by weighing the
masses of the acids given in Table 1 into 100 ml volumetric
flasks and filling them up to the mark with distilled water.
Table 1: The masses of the carboxylic acids R-COOH to be
weighed out for 0.1 molar solutions.
Connect the control input for manual key button of the motor
piston burette to the TTL-output of the Cobra3 Chem-Unit with
the cable supplied for this particular purpose. Connect the pH
electrode to the pH-input, and the temperature probe to tem-
perature input T1 of the Chem-Unit.
Call up the Measure programme in Windows and enter <Chem-
Unit> as measuring instrument. Set the measurement parame-
ters as shown in Fig. 2. Select <pH (comp T1)> as mode in
<Preferences> under <pH/Potential>. Set the display range to
1-13 in menu prompt <Displays>. Set Digital display 1 to <pH
value>, and select, under Diagrams, <Line diagram> for
Diagram 1, <pH value> for Diagram 1a, <0 - 10 ml> for the dis-
play range and <no auto range>. Confirm your entries with
<OK>.
Now calibrate your pH electrode using two buffers. To do this,
enter the appropriate pH value in <pH/Potential> under the
menu prompt <Calibrate>, dip the electrode into the buffer and
save with <Calibrate>. To calibrate the temperature sensor,
either balance it against a temperature measured with a ther-
mometer, or with the level of a temperature probe connected to
T2 or T3.
After having made all settings, press <Continue> to reach the
field for the recording of measured values. Arrange the displays
as you want them.
Follow the operating instructions supplied with the motor piston
burette to fill it with 0.1 molar sodium hydroxide solution. Set the
motor piston burette to <Dosing>, <Nom. volume = 0.25 ml>
and <Speed = 99.99 ml/min>.
Fill 60 ml of distilled water into a 150 ml glass beaker and add a
magnetic stirring bar. Pipette 5 ml of the carboxylic acid solution
that is to be titrated into the beaker. Cut the rubber stopper with
central hole lengthwise from one side to the hole and fit the tem-
perature probe into it. Fix the dispensing tip of the motor piston
burette, together with the pH electrode and the temperature
probe, in the electrode holder. Ensure that the sensing
diaphragm of the pH electrode is covered by the solution.
Adjust the magnetic stirrer to an intermediate stirring speed,
then push <Start measurement> to begin the titration. The first
measurement (for V = 0.0 ml) is immediately recorded, following
which the motor piston burette dispenses the first portion of
sodium hydroxide solution. The titration now proceeds accord-
ing to the parameters that have been set. It is automatically
stopped after 10 ml of sodium hydroxide solution have been
added. On completion of the series of measurements, save the
data with <File><Save measurement as...>.
Thoroughly rinse the beaker and the pH electrode with distilled
water after each titration.
Fig. 3 shows the graph as presented by the programme after
having stopped the measurement. To have the equivalence point
and the pK displayed, use <Detect point of equivalence...>
under the menu prompt <Analysis>.
Theory and Evaluation
Carboxylic acids R-COOH are weak electrolytes, which are only
partially dissociated in aqueous solutions, i.e.
R-COOH R-COO
-
+ H
+
PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3030940 2
LEC
03.09
Dissociation equilibrium
Fig. 2: Measurement parameters
Acid R Mass in g
Formic acid H 0.460
Acetic acid CH
3
0.601
Monochloracetic acid CH
2
Cl 0.945
Propionic acid C
2
H
5
0.741
Propionic acid CH(OH)CH
3
1.001
n-Butyric acid C
3
H
7
0.881
Fig. 3: Determination of the pK
a
value of formic acid from the
neutralisation curve
The position of the dissociation equilibrium is quantatively char-
acterised by the dissociation or acid constant Ka or the pKa
value, from which it is derived.
(1)
(a
i
= activity of the substance i. In extremely diluted solutions
with intermolecular or interionic interactions which can be
neglected, it is equal to the concentration c
i
)
pK
a
= - log K
a
(2)
When the formulation (2) and the analogous definition of the pH
value are taken into consideration and the logarithm is taken, the
Henderson-Hasselbalch equation (3) is obtained from (1). This
new equation describes the correlation between pH value and
the composition (c
R-COOH
/ c
R-COO-
) of buffer systems or the pro-
portion of both forms on the total concentration (c
0
= c
R-COOH
+
c
R-COO-
) of the weak acid for a given acidic strength (pK
a
).
(3)
During the successively neutralisation of a weak acid, c
R-COO
-
corresponds virtually to the concentration of the salt formed. In
contrast, the equilibrium concentration c
R-COOH
is identical to the
remaining total acid concentration c
0
.
If half of the acid has reacted (half neutralisation), it follows that
c
R-COOH
= c
R-COO
- and (3) becomes (3.1).
pK
a
= pH (3.1)
The pK
a
value of a weak acid is thus equal to the pH value at
half neutralisation. This can be potentiometrically determined via
the measurement of the cell voltage U between a hydronium-
ion-sensitive electrode (glass electrode) and a reference elec-
trode (silver chloride electrode), which are available in combina-
tion as single-rod glass electrodes (measuring chains).
Subsequent to calibration with buffer solutions of known pH, the
linear relationship between pH and U in the measuring sequence
in the glass electrode:
U = const. pH + const. (4)
is saved in the Cobra3 Chem-Unit, so that the pH values that
correspond to the measured cell voltages can be immediately
displayed.
On completion of the titration, the pK
a
value can be directly
determined from the neutralisation curve at half neutralisation by
means of equation 3.1.
At constant temperature and for the same solvent, K
a
and pK
a
are a function of the nature of the residue (substituent) R.
Consequently, compared to R = CH
3
, electron-attracting sub-
stituents (acceptors) such as R = CH
2
Cl lead to a facilitated dis-
sociation of the proton via a depression of the electron density
within the carboxyl group (-I effect) and thus to an elevation of
the acid constant K
a
or a decrease in the pK
a
value. In contrast,
electron-repelling substances (donors) such as R = C
2
H
7
result
in a reduction of the acidic strength via a +I effect.
The polar substituent influence can be quantified by empirical-
ly determined substituent constants s* which correlate in a
statistically significant manner with the determined pK value
(Fig. 3). The s* constants, which are interesting in this context,
are given in Table 2 together with the pK values of the investi-
gated carboxylic acids (taken from the chemical literature) for
T = 298 K.
Table 2: Literature values for the pK
a
values (T = 298 K) of
selected Carboxylic acids R-COOH and their polar sub-
stituent constants.
Data and results
Fig. 2 shows the neutralisation curve for the titration of approxi-
mately 0.1 molar formic acid with 0.1 molar NaOH. A value of
3.74 is obtained for pK
a
, and this agrees well with the literature
value given in Table 2 for T = 298 K. The analogously determined
pK
a
values of the other carboxylic acids are shown as a function
of their polar substituent constants in Fig. 3.
pK
a
pH
c
RCOOH

c
RCOO

K
a

a
RCOO
a
H

a
RCOOH

c
RCOO
c
H

c
RCOOH
PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3030940 3
LEC
03.09
Dissociation equilibrium
R pK
a
s*
H 3.75 0.490
CH
3
4.76 0.000
CH
2
Cl 2.85 1.050
C
2
H
5
4.86 -0.100
CH(OH)CH
3
3.86 0.450
C
3
H
7
4.83 -0.115
PHYWE series of publications Laboratory Experiments Chemistry PHYWE SYSTEME GMBH & Co. KG D-37070 Gttingen P3030940 4
LEC
03.09
Dissociation equilibrium

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