Silesian University of Technology

FACULTY OF CHEMISTRY
DEPARTMENT OF PHYSICAL CHEMISTRY AND
TECHNOLOGY OF POLYMERS

valid for academic year 2017/2018

DETERMINATION OF THE ACID-BASE EQUILIBRIUM

CONSTANT IN AQUEOUS SOLUTIONS

Tutor: Karolina Gębka

Place: Department of Physical Chemistry and

Technology of Polymers,
Room 210

PHYSICAL CHEMISTRY LABORATORY

I. Theoretical introduction

Some organic compounds, weak acids or weak bases, exhibit color difference between their acid and
alkaline forms. Structural changes occurring as a result of proton attachment or proton removal may change the
spectral characteristics of the compound. Both removal and attachment of a proton cause damage to the
electronic structure of the original compound, which in turn lead to the formation of a number of possible
mesomeric forms, characterized by different color than the starting compound. As a result, by using the
spectrophotometric measurements and Bouguer - Lambert – Beer law, it is possible to study chemical
equilibrium involving these compounds, experimentally. Some of them have been widely used as acid-alkaline
indicators (pH indicators).
The compound whose molecules can give a proton is called acid (HA), base is the compound (B), whose
molecules can accept the proton. Each acid corresponds to a conjugate base and each base corresponds to its
conjugated acid, according to the scheme:

acid ⇔ base + H+ (1)

Acid (HA), which is dissolved in water, reacts with it according to the equation:

HA + H2 O ⇔ A- + H3O+ (2)

The process of acid dissociation can be presented as below:

HA ⇔ H+ + A- (3)

Bear in mind that H+ is in fact a hydrated proton H3O+.

The thermodynamic equilibrium constant for reaction (3) is called the acid constant:

a H .a A .
+ −
(4)
Ka =
a HA
where:
aA- - activity of base
aHA - activity of acid

In alkaline solutions, water gives the proton to the base, which can be denoted by the following equation:

B + H2O ⇔ HB+ + OH- (5)

The dissociation constant, called a basic constant, is defined by the equation:

a HB a OH
+ −
(6)
Kb =
aB
where:
aHB+ - activity of acid
aB - activity of base
Compounds reacting as both acid and base are called ampholytes. Water is the example of an ampholyte. The
dissociation reaction of water can be denoted by the equation:

2H2O ⇔ H3O+ + OH- (7)

or in a simplified form:

H2O ⇔H+ + OH- (8)

Using the water equilibrium dissociation constant Kw specified for equation (8), and on the basis of equations (4)
and (6) it can be concluded that for the same pair of conjugate acid- base (A-B) there is a relationship:

K w = Ka Kb (9)

The activity of acid or base is not easy to calculate, especially when the exact electric charge of A or B is not
known. Therefore, in practice we often use so called "mixed” (activity - concentration) constants described by
the equations:

a H . cB
=
+

ka .
(10 a)
cA
=
cOH .cA −

kb .
(10 b)
cB
k W = a H ⋅ cOH+
.
−
.
(10 c)

After logarithming both sides of equation (10a), and assuming that:

pka = -log ka, pH = -log a H+, we obtain Hasselbalch equation:

pH = p k a + log cB (11)
cA
Since the sum of the equilibrium concentrations of the acid and alkaline form is always constant and equal to the
initial concentration (c) of acid-base pair:

C = C A + CB (12)

equation (11) can be written in a different form:

pH = p k a + log cB = p k a + log
c − cA (11 a)
c − cB cA
Equations (11) or (11 a) are the theoretical basis for the experimental determination of the equilibrium
acid - base constant, pka of a given compound, which is the aim of this exercise. This is because if we change the

pH of the solution, a change in the ratio of equilibrium concentrations in logarithmic term will also be changed.
Knowing the pH and the corresponding value of the equilibrium concentration of the one of the colored forms of
the compound (cA or cB), and the initial concentration (c) of the compound, we can calculate the value of pka,

and hence the acid - base equilibrium constant.

 As it was mentioned earlier, Bouguer - Lambert - Beer law allows the accurate determination of the
concentration of colored compound in the solution by measuring the absorbance A(λ1)A by means of

spectrophotometer:

A (λ1)A = ε (λ1)A cA l (13)

where:
ε(λ1) - molar absorption coefficient (dm3 / mol cm) of the colored form of A,

measured at a given wavelength λ1,

cA - concentration (mol / dm3) of the colored form of A,

l - optical path (cm)

A similar relationship as equation (13) can be written for the colored form of B, wherein the maximum
absorbance is at a different wavelength λ2. The use of previously derived relations enables to express equations

(11) and (11a) by measured values:

pH = p k a + log
A (λ )B ε (λ )A
2 1
(14)
A (λ )A ε (λ )B
1 2

A (λ )B A (λ )A − A (λ )A
0
2 1 1
pH = p k a + log 0 = p k a + log
A (λ )B − A (λ )B2 2
A (λ )A 1
(15)
This allows to determine the value of pka using calculation method as the arithmetic mean of the measurement

series. A0(λ1)A and A0(λ2)B represent the absorbances measured for the solutions with such high or low pH so

that there is practically only one colored form of A or B, respectively. This follows from the equations (12) (13)
and (14).
The determination of pka is also possible with the use of a graphical method. Rearranging equations (14) and
(15) we obtain:

log
A (λ )A ε (λ )B = p − pH
1 2
k (16)
A (λ )B ε (λ )A
2 1
a

0
( )− ( ) ( )
log λ 2 B A λ 2 B = log 0 A λ1 A
A = p k − pH (17)
( )
A λ2 B ( ) ( )
A λ1 A A λ1 A
− a

If we put the value of the left side of equation (16) or (17) on the axis of ordinate (y-axis), and the values of pH
on the abscissa axis (x-axis), we obtain a straight line with a slope equal to 1; the length of as-formed segment is
equal to pkA. It should be noted that if we want to use the equation (16), we must perform measurements at two
different wavelengths, and know or calculate the molar absorbance coefficients of A and B at these wavelengths.
In the case of equation (17) it is not necessary.
If the absorbance maxima for colored forms of A and B are too close to each other, then there is a partial overlap
between the absorbance bands of both colored forms. In this case, the measured absorbance of the solution at λ1
and λ2 does not correspond to the concentration of only one colored form of A or B, and equation (14), (15),

(16) and (17) cannot be used. It should be noted that this is a very common case. Using the law of additivity of
absorbance of solutions, we can write the following expressions:

A(λ1 ) = A(λ1)A + A(λ1)B = ε(λ1)A cA l + ε(λ1)B cB l (18)

A(λ2) = A(λ2)A + A(λ2)B = ε(λ2)A cA l + ε(λ2)B cB l (19)

If we consider the equation (12) and the relationships:

A0 (λ2)A = ε (λ2)A c l (20)

A0 (λ1)B = ε (λ1)B c l (21)

basing on equations (18) and (19) we obtain:

A (λ1) − A0 (λ1)B
cA = [ε( ) − ε( ) ]l (22)
λ1 A λ1 B
A (λ 2)A − A (λ 2)
0

cB = [ε( ) − ε( ) ]l (23)
λ2 A λ2 B
Substituting (22) and (23) into equation (11) we obtain:

  
( )
0
( )
A λ1 − A λ1  ε λ 2 − ε λ 2  ( ) ( )
log  B  A B
= p k a − pH (24)
 0  
( ) ( ) ( )
A λ 2 − A λ 2  ε λ1 − ε λ1  ( )
 A  A B

If we want to carry out the measurements at only one wavelength ( λ1 or λ2), similarly as in equation (17), then

we need to use equations (22) and (23) and the relationships:

A0 (λ1)A=ε (λ1)A c l (25)

A0 (λ2)B=ε (λ2)B c l (26)

Equation 11a looks like:

 
( )
A λ1 − A0 λ1  ε λ1 ( ) ( )
 B  A
log = p k a − pH (27)
   
( ) ( ) ( )
ε λ1 − ε λ1  A0 λ1 − A λ1 − A0 ( ) ( ) ( )
λ1 ε λ1
 A B
 A 
 B A
or
    
( ) ( ) ( )
ε λ 2 − ε λ 2  A 0 λ 2 −  A λ 2 − A ( ) (λ2)ε(λ2)
 B  B  
log  A A B
= p k a − pH (28)
 0 
( )
A λ 2 − A λ 2  ε λ 2 ( ) ( )
 A  B

II. Experimental section

Equipment:
spectrophotometer, glass cuvettes, pH-meter with electrode

Reagents:
Britton – Robinson buffer solution (0.04 M CH3COOH + 0.04 M H3PO4 + 0.04 M H3BO3),
0.2 M NaOH, 0.2 M HCl.

Before starting the spectrophotometric measurements, a series of buffer solutions with given pH values should
be prepared in conical flasks according to this instruction: Add the specified volume of 0.2 M NaOH to 50 ml of
buffer solution and measure the pH of the solution according to the instruction. Pour 1 ml of the sample solution
to five clean 25 ml flasks and fill the volume with a solution of a proper pH. You should obtain the series of
sample solutions of increasing pH but with the identical concentration of sample. Note that the color of each
solution should be different from the others. In addition, pour 1 ml of the sample solution to two clean 25 ml
flasks and fill the volume with 0.2 M NaOH or 0.2 M HCl solutions. In this way, two solutions of the sample,
one containing only its alkaline form and the other one containing only the acidic form, are obtained. The colors
of these solutions should be evidently different. Turn on the spectrometer according to the instruction.
At the beginning of measurements, rinse the cuvettes thoroughly with distilled water. Then, fill one cuvette with
distilled water and use it to reset the spectrophotometer. Rinse the other cuvette with a solution of the sample in a
given pH buffer and then fill it with this solution. Finally, measure the absorbance at a given wavelength. It
should be noted that both the reset of the device and the measurement are performed at the same wavelength.
Then, remove the sample solution from cuvette and wash it with distilled water. Before filling the cuvette with
another sample buffer, rinse it with the same solution, reset the device and repeat measurement in a way
described above. At the end, measure the absorbances of a sample solution in 0.2 M HCl (A0A) and 0.2 M NaOH
(A0B), taking as a reference 0.2 M HCl and 0.2 M NaOH, respectively. The results should be written in the form
of a table (see paragraph 4 of this manual).
After finishing the measurements, stop the instrument immediately and wash the cuvettes and glassware
carefully.
III. Safety rules and waste disposal
Substance Classification Hazards First aid information Disposal
In case of skin contact, remove contaminated
clothing, wash with water.
Sodium Substance is
Causes severe skin In case of contact with eyes, rinse with plenty Place in container for
hydroxide corrosive to
burns and eye damage. of water, immediately seek medical advice. disposal S.
NaOH skin.
When ingested do not induce vomiting, seek
medical advice immediately.
In case of skin contact, remove contaminated
clothing, wash with water.
Hydrochloric Substance is
Causes severe skin In case of contact with eyes, rinse with plenty Place in container for
acid corrosive to
burns and eye damage. of water. disposal S.
HCl skin.
In case of swallowing: drink plenty of water,
avoid vomiting.
In case of skin contact, remove contaminated
Substance is clothing, wash with water.
Acetic acid Causes severe skin Place in container for
corrosive to In case of contact with eyes, rinse with plenty
CH3COOH burns and eye damage. disposal O.
skin. of water.
In case of swallowing: avoid vomiting.
In case of swallowing: avoid vomiting.
Phosphoric Substance is In case of skin contact, remove contaminated
Causes severe skin Place in container for
acid corrosive to clothing, wash with water.
burns and eye damage. disposal S.
H3PO4 skin. In case of contact with eyes, rinse with plenty
of water.
In case of skin contact, wash with water.
Substance is In case of contact with eyes, rinse with plenty
Boric acid Place in container for
toxic for May damage fertility. of water.
H3BO3 disposal S.
fertility. In case of swallowing: drink plenty of water,
seek medical advice.
In case of skin contact, remove contaminated
clothing, wash with water.
Substance is Toxic if swallowed. In case of contact with eyes, rinse with plenty Place in container for
Sample
toxic. Irritating to eyes. of water. disposal O.
In case of swallowing: drink plenty of water,
seek medical advice.

IV. Analysis of results

The results of measurements, calculations and other data, are presented in the form of the table:
λ =................. nm
εA =...................(dm3 / mol cm)
3
εB =.................. (dm / mol cm)
AA0 =...................
AB0 =...................
T =.....................(K)
No. pH of
examined Absorbance of solution Value of the logarithmic term pka
solution

The report should include the value of pka obtained as a results of the calculation method and carefully

constructed A4 plot, necessary to determine the value of pka by means of a graphic method..
V. Typical questions

1. Describe acid-base equilibrium in aqueous solutions.

2. Discuss the influence of temperature on the equilibrium constant of the reaction.
3. Discuss Bouguer - Lambert – Beer law and its applications.
4. Prove that equations (27) and (28) are a special case of more general equations (16) and (17).
5. List the main causes of errors in spectrophotometric measurements.

VI. Literature

1. P. W. Atkins: Physical Chemistry, 4th Edition, Oxford University Press,

2. Donald A. McQuarrie, John D. Simon, John Choi, Physical Chemistry, University Science
Books1997
3. Metiu Horia, Physical Chemistry, Taylor & Francis Inc, 2006