Experiment 2: Acid / base titration

cunknown = 62.0 ± 0.5 mM @ 95% confidence level

Nikolai Skrynnikov
TA: Boone Prentice
Section number: 1
25 Jan 2008 (data courtesy of Ike Fehrenbacher, 2004)

1
Introduction

This laboratory exercise relies on a titration technique to determine an unknown

concentration of monoprotic acid in solution. In the process of titration, a basic solution is
gradually added to the acidic solution until complete neutralization is obtained. The ‘end
point’ of the titration is detected with the help of an indicator as color of the solution
changes upon neutralization.
By measuring the volume of the titrant required to reach the ‘end point’, it is
possible to relate the concentration of the acid to the concentration of the base. In this
manner, the unknown concentration can be expressed through the known concentration.
The concentration determination is repeated several times in order to improve the
precision of the measurements and to estimate the experimental error.

Results and discussion

The experiment involves two steps: (i) Standardization of sodium hydroxide (NaOH)
solution using potassium hydrogen phtalate (KHP) solution, and (ii) titration of an
unknown monoprotic acid solution using the standardized NaOH solution. The two steps,
(i) and (ii), are essentially similar. Therefore, only the first step is briefly described
below. The neutralization reaction proceeds as follows:
NaOH + KHP → Na+ + K+ + P2- + H2O
Once this reaction is complete, an excess of NaOH starts building up, triggering the
response from the indicator:
NaOH + HIn(colorless) → Na+ + In-(pink) + H2O.

An interesting question is why NaOH first reacts with KHP and only then, after
KHP is consumed, it starts reacting with HIn. At this point I do not know the answer, but
hope that this question will be addressed later in class.
Another question arises as to why step (i) is needed at all. Indeed, one could
envisage a simpler measurement scheme where the solution of NaOH is prepared with
known concentration and used to titrate an unknown acid. Bear in mind, however, that
NaOH is a poor primary standard: it is highly hygroscopic, chemically unstable (reacts
with CO2 of air), typically low-purity (if purchased cheap), and has low molecular weight
(which leads to higher relative error when the compound is weighed out). Conversely,
KHP has many desirable characteristics which make it a good primary standard. This
dictates a choice of the two-step scheme, with KHP as a primary standard and NaOH as a
secondary standard.

2
Standardization

For the standardization step, the KHP solution has been prepared by weighing out
4.8149 g of (dried) KHP and dissolving it in distilled water to a volume of 250 mL.
Considering that the molecular weight of KHP is MWKHP = 204.23 g/mol, the
concentration of the KHP solution is:
⎛ 4.8149 [g] ⎞
cKHP = ⎜ ⎟ 0.250 [L] = 0.0943035 [M] = 94.3035 [mM]
⎝ 204.23 [g/mol] ⎠
The titration (standardization) results using 25.00 mL aliquots of the KHP
solution are summarized in Table 1 below.

Trial 1* Trial 2 Trial 3

Initial volume [mL] 1.50 0.50 24.60
Final volume [mL] 25.50 24.55 48.52
end - point
Volume added VNaOH [mL] 24.00 24.05 23.92

Table 1. Volume data from NaOH standardization measurements using KHP solution.
The data are obtained from the buret readings.
* Trial 1 was preceded with the scout titration (trial 0). The results from the scout titration are
not included in this table since they are not quantitatively accurate.

Already a cursory inspection of Table 1 shows that the results are highly
reproducible – the uncertainty in the volume of the titrant is on the order of 0.1 mL
(0.4%).
The data from Table 1 can be used to determine the concentration of sodium
hydroxide solution, cNaOH . The molar balance conditions corresponding to the complete
neutralization (end point of the titration) can be written as:

end - point
cKHP [mol/L] VKHP [L] = cNaOH [mol/L] VNaOH [L]

The concentration cNaOH can be calculated on the basis of this formula, using
cKHP = 94.3035 mM , VKHP = 25 mL , and VNaOH
end - point
as listed in Table 1. The values of
i
cNaOH calculated in this manner are 98.2328, 98.0286, and 98.5614 mM for trials i = 1, 2,
and 3, respectively. The mean concentration, cNaOH , is 98.2742 mM.

The uncertainty in cNaOH is reported according to the standard recipe:

3
 ts
cNaOH = cNaOH ±
N
where
N

∑ (c i
NaOH − cNaOH ) 2
s= i =1
.
N −1

Here N is the number of measurements, N = 3 , and t is the so-called ‘Student’s

coefficient’, t = 4.30 assuming that the confidence level is 95% and that the number of
degrees of freedom is N − 1 = 2 . The sample standard deviation, s , was calculated
i
according to the above formula using the data from the individual trials, cNaOH , and their
mean, cNaOH . This calculation produced s = 0.2688 mM .
After rounding off the result and retaining the significant digits I obtained:

cNaOH = 98.3 ± 0.7 mM @ 95% confidence level

The concentration of sodium hydroxide obtained in this fashion is further used to

determine the concentration of the unknown.

Titration of the unknown

The titration results using standardized NaOH solution are listed in Table 2.

Trial 1* Trial 2 Trial 3

Initial volume [mL] 16.60 0.60 16.40
Final volume [mL] 32.30 16.40 32.18
end - point
Volume added VNaOH [mL] 15.70 15.80 15.78

Table 2. Volume data from the titration of unknown monoprotic acid using standardized
NaOH solution. The data are obtained from the buret readings.
* Trial 1 was preceded with the scout titration (trial 0). The results from the scout titration are
not included in this table since they are not quantitatively accurate.

The subsequent calculations follow exactly the same steps as described above in the
‘Standardization’ section. The balance condition at the end point of the titration is now

4
used to determine the concentration of the unknown, cunknown = cNaOH (VNaOH
end - point
/ Vunknown ) .
The volume Vunknown used in this titration is 25 mL.

The concentration cunknown determined in this fashion is the main result of this study:

cunknown = 62.0 ± 0.5 mM @ 95% confidence level

Control questions:

(a) Why it is necessary to measure volumes very carefully when preparing the KHP
solution (solution 5), but NOT necessary to measure volumes too carefully when
preparing the dilute NaOH solution (solution 4)?
The molarity of the dilute NaOH solution, cNaOH , is not determined from the volumes of
the concentrated NaOH solution and water added together. Instead, it is determined via
the KHP titration. On the other hand, the molarity of KHP solution, cKHP , is determined
based on the mass of the KHP and the volume of water it is dissolved in.

(b) Why in step 2 should the pipet and beaker be rinsed with the KHP solution (not with
distilled water), whereas the Erlenmeyer flasks should be rinsed with distilled water (not
with the KHP solution)?
Using the distilled water for rinsing may cause (unwanted) dilution of the KHP solution,
and hence it is better to wash with the same KHP solution.
The situation with the Erlenmeyer flask is different. It is only important that 25
mL of KHP solution with concentration cKHP are transferred to the Erlenmeyer flask. At
this point, extra water left on the walls of the Erlenmeyer flask does not matter. Indeed,
addition of water does not change the number of KHP molecules in the flask and,
therefore, has no effect on the calculation of cNaOH .
On the contrary, rinsing the flask with KHP solution would increases the number
of KHP molecules in the flask and thus compromise the method.

(c) Give at least two reasons why it is better to read the initial volume of a buret than to
adjust the volume to some round value such as zero.
First, it is generally impossible to achieve a good accuracy by trying to fill a buret to
some round value (human hands are not steady enough for this purpose). Reading the
volume of a buret is more accurate (eyes are a more reliable instrument). Second, trying
to fill a buret to a round value is time-consuming. Indeed, one has to add solution to a
buret in small increments, constantly checking the resulting fluid level.

5
Conclusion

This study demonstrates that the titration method relying on visual detection of the end
point allows for fairly precise determination of the unknown concentration (relative error
less than 1%). Both bases and acids can be analyzed in this manner, as illustrated in this
report: cNaOH = 98.3 ± 0.7 mM and cunknown = 62.0 ± 0.5 mM (confidence level 95%). The
precision and accuracy of the method can be improved by (i) fitting the buret with an
electronic device to control the flow of the fluid, (ii) using a spectrophotometer to detect
the color change at the end point of the titration, and (iii) using a special small-volume
chamber where two solutions – basic and acidic – can be rapidly mixed in order to
prevent a time lag from slow diffusion.