BRUNO ROBERTO REIS ALVES

IRV BREW

CON-1: CONDUCTANCE TITRATION OF VANILLA

REPORT

EXPERIMENT PERFOMED IN 03/11

REPORT DUE TO 04/01

Abstract
The conductance titration was used as the technique to investigate the reactions between
vanillin and NaOH. The analysis showed that the conductance of a solution is related with the
concentration of the interest analyte so an equation was created to understand this behavior.
Using visual and statistical methods, it was possible to find the endpoints of the reaction and
calculate the concentration of vanillin in the unknown sample, (3.50.3) g L-1 using the visual
method and (3.450.03) g L-1 using the statistical approach.

Introduction/Experimental Methods

The ability of a solution to conduct electricity is determined by the concentration and

mobility of ions in the solution and by the charges carried by those ions. Conductivity is a
measure of the number of mobile ions per unit volume in a solution (MicroLAB, 2003). The
conductometric analysis is based on measurement of the electrical conductance of a solution
from which, by previous calibration, the analyte concentration can be derived (DAHMEN, 1986)
so, the technique can be used to follow a chemical reaction, as a titration.
The conductance of an electrolyte solution changes as a function of the concentration of
mobile charge-carrying ions. Consequently, when this concentration changes during a titration
because of the chemical reaction between one solution constituent and the titrant, the
conductance will chance accordingly (HOLZE, 2009). This change can be employed to detect
the equivalence point in a titration to observe the chemical reaction studied. According to
Glasstone (2013), the determination of the end-point of a titration by means of conductance
measurements is known as conductometric titration. The conductance readings corresponding to
various added amounts of titrant are plotted against the latter. Since the variation of conductance
is linear, it is sufficient to obtain readings covering the range before and after the end-point, and
to draw two straight lines through them; the intersection of the lines gives the required end-point.
For this procedure it was utilized 0.1 mol L-1 of hydrochloric acid, HCl, standard and 0.1
mol L-1 of sodium hydroxide, NaOH (the solution of NaOH was diluted from 3.0 mol L-1). To
standardize the NaOH solution, 10 mL of standard HCl were pipetted into 1L beaker containing
500 mL of water. After the preparation of the reagents, the computed based acquisition tool
MicroLab was set to measure conductance of the stirred solution, at 2 mL increments of titrant
(HCl standard), up to 20 mL. This analysis was made in duplicate.

After that, a graph was plotted (conductance vs. mL titrant). The endpoint were
determined and the real molarity of NaOH was calculated.
To analyze the conductance of vanillin, 50 mL aliquots of unknown vanillin solution
were pipette into 1 L beaker containing 500 mL of water. The final volume was titrated as the
standardization in increments of 1 mL up to 5 mL and 2 mL up to the end of analysis (25 mL). A
graph was plotted, the endpoints were determined and the concentration (in g L-1) of vanillin in
the unknown sample was calculated.

Results

Sodium hydroxide is a strong base that reacts with hydrochloric acid, a strong acid, to
give a neutral salt, the reaction represented in Figure 1.

Figure 1. Reaction between NaOH and HCl

The titration of NaOH was made to reach a standardization of this reagent; the
dependence of conductance of NaOH with volume of 0.1 M HCl standard was analyzed and
plotted, represented in a graph, Figure 2. The highly conducting hydrogen ions initially present
in the solution are replaced by sodium ions having a much lower conductance, that is, the salt
formed has a smaller conductance than the strong acid from which it was made (GLASSTONE,
2013). After the neutralization, the conductance increase, since the OH- are no longer used up in
the reaction.

Figure 2. Conductivity of the solution vs. volume of titrant

In the V-shaped plot of conductance vs. volume of added titrant solution the equivalence
point can be identified easily at the minimum of the curve (HOLZE, 2009). According to Figure
2, the endpoints of both replicates are close to 10 mL, the point when the conductivity ends to

decrease and starts to increase. Consequently, the end point could be seen as (10.00.5) mL.
Since the additions were made in 1 mL increments, it could be possible to affirm that the error
for this measure is a half of 1 mL, 0.5 mL.
However, it could be not much precise to define the endpoint only by looking the graph
(visual method), it could be necessary, also, a statistical study of the dependence of conductivity
with volume of titrant. Analyzing the graphs, it was possible to realize that they have similarities
with a piecewise linear function. According to Stanley (2005), a piecewise linear function is a
real-valued function whose graph is composed of straight-line sections, so an equation was
created, trying to understand the relation between volume of titrant and conductivity of solution,
in order to obtain the end point of the reaction using statistic data. This end point could be
characterized as the point at the intersection of two segments, the section of decrease and the
section of increase of conductivity. The Figure 3 represent the function proposed, where x1 is the
initial volume of titrant, x2 is the final volume of titrant, x3 is the volume used to reach the endpoint, y1 is the initial conductivity, y2 is the final conductivity measured in the analysis and y3 is
the conductivity when the reaction reach the end-point.

Figure 3: Piecewise linear function proposed

When the analysis was replicate, the first point shown an unusual comportment, since the
value of the conductance for this point was determined to be less than the conductivity observed
with the addition of titrant. This happened due to the fact the conductivity sensor has not been
completely dipped in the solution before the reading of the equipment. For that reason, the point
0 mL of both replicates was deleted for the regression analysis, because extreme points affect the

proposed equation. Therefore, a non-linear fit, using the equation proposed, was made to try to
have a better comprehension about the study, and it was represented by Figure 4.

Figure 4. Non-linear regression fit of conductivity of reaction vs. volume of titrant

The table 1 represents the coefficients obtained after the non-linear regression
represented by Figure 4. By this method, the endpoint was reached at (9.50.2) mL of 0.1 M HCl
standard, with a coefficient R2 of 0.99374 and 0.99982. The statistical method has
demonstrated its efficiency in describing the behavior of the reaction since presented a value of
R2 very close to 1, an indicative that the proposed equation showed an excellent fit and could be
used to understand what really happened in the acid-base reaction analyzed.
Table 1. Statistical values for the non-linear regression fit
Graph

X1 (mL)

Y1 (S)

X2 (mL)

Y2 (S)

X3 (mL)

Y3 (S)

4399

20

4988

9.50.2

1676

6632

20

6911

9.380.03

2381

With this result is now possible to calculate the concentration of the NaOH and
standardize it. The table 2 shows the results using the Visual method and the Statistical
method, where V is volume of titrant used, in mL, and c is the concentration of NaOH titrate, in

mol L-1. It is possible to see that the concentration of NaOH was (0.1000.005) mol L-1 using the
visual method, and (0.1050.002) mol L-1 using the statistical method.
Table 2. Concentration of NaOH by visual and statistical methods
Method

V (mL)

c (mol L-1)

Visual

(10.00.5)

(0.1000.005)

Statistical

(9.50.2)

(0.1050.002)

The same approach was used to analyze the unknown sample, containing vanillin,
reacting with NaOH, as Figure 5.

Figure 5. Mechanism of reaction between vanillin and OH- Source: WELLS

In this case, however, the comportment of the conductivity is different that observed
when strong acid reacted with strong base; the OH- ion deprotonate vanillin, giving as a result a
molecule with a negative charge. This charge affects the conductance of the solution, since this
property is dependent on charges present in the system, causing an increase in the conductance
with the addition of NaOH in the reaction. Thus, with more OH-, more vanillin will be
deprotonated, and a higher conductance will be perceived.
The Figure 6 shows the behavior of the unknown sample when titrate with NaOH,
previously standardized.

Figure 6. Conductivity of the solution vs. volume of titrant

At this time, it was difficult to use the visual method to have an idea where is the endpoint; this analysis did not show any inversion point as in the standardization of NaOH.
However, it is possible to make mathematical manipulations to transform the data in a way that
would be effective to use the visual method to find the endpoint. The manipulations chosen to
transform the values were the first and the second derivative, as shown in Figure 7. The
derivative is very useful in titration analysis; according to Athawale and Mathur (2001), it helps
to accurate the representation of the equivalence point.
a

Figure 7. Graph of first derivative (a) and second derivative (b) of conductivity against volume of titrant

After the derivative transformations the analysis using visual methods turned easier; it
turned possible to see a great difference in the comportment of the points before reach the
equivalence point and after the end point. Therefore, the end point was (111 mL) of NaOH, the
titrant used. (Near to the end point, the increments of NaOH was 2 mL).
For a statistical approach, the equation proposed was used again, to study the behavior of
the unknown sample conductivity versus increments of NaOH. The Figure 8 shows the curve
fitted after the non-linear regression analysis.

Figure 8. Non-linear regression analysis of unknown sample

The results that were found after the statistical analysis represented in Figure 8 were
organized in the Table 3. The regression showed a coefficient R2 of 0.99984 and an equivalent
point at 10.70.1 mL of NaOH.
Table 3. Statistical values for the non-linear regression
Unknown Sample

X1 (mL)

Y1 (S)

X2 (mL)

Y2 (S)

X3 (mL)

Y3 (S)

Vanillin

42

25

7132

10.70.1

1585

With this result is now possible to calculate the concentration of vanillin in the unknown
sample. The table 4 shows the results using the Visual method and the Statistical method,
where V is volume of titrant used, c is the concentration of vanillin in mol L-1, and is the
concentration of vanillin in g L-1 in the sample.
Table 4. Concentration of vanillin in the unknown sample
Method

V (mL)

c (mol L-1)

(g L-1)

Visual

(111)

(0.0230.002)

(3.50.3)

Statistical

(10.70.1)

(0.02270.0002)

(3.450.03)

It is possible to see that the concentration of vanillin in the unknown sample was 3.50.3
g L-1 using the visual method, and 3.450.03 g L-1 using the statistical method.

Calculations

The following equations were used and the necessary calculation were performed. Figure
9 and table 4 represent the equation of dilution of NaOH, from 3 mol L-1 to 0.1 mol L-1, where c1
is concentration of concentrated NaOH, V1 is the volume of concentrated NaOH used for the
dilution, c2 is the concentration of diluted NaOH and V2 is the final volume of the solution, and
the table X, the values used for the calculation.

Figure 9. Dilution of NaOH

Table 4. Dilution of NaOH
Dilution

c2 (mol L-1)

V2 (mL)

c1 (mol L-1)

V1 (mL)

NaOH

0.1

250

8.3

After the conductometric standardization, the concentration of NaOH was calculated,

using the visual method and statistical method to find the endpoint of the titration. The
Figure 10, and table 5, represent that calculation, where cNaOH is the real concentration of NaOH,
VHCl is the volume on the end-point, cHCl is the concentration of the standard HCl and VNaOH is
the volume of the titrate.

Figure 10. Titration of NaOH by standard HCl

Table 5. Titration of NaOH by standard HCl
Method

cHCl (mol L-1)

VHCl (mL)

VNaOH (mL)

cNaOH (mol L-1)

Visual method

0.1

10

(10.00.5)

(0.1000.005)

Statistical method

0.1

10

(9.50.2)

(0.1050.002)

The concentration of NaOH was calculated with the propagation of uncertainty, figure 11
(SKOOG, 2007), where a is the volume on the end-point, y is the concentration of NaOH and
S is the standard deviation of it respective subscript value; for the visual method, the standard
deviation of the volume was a half of the near increments volume (increments of 1 gives a
deviation of 0.5), and the deviation for the statistical method was calculated using OriginPro 9.0.
In the table 6 is shown the values used for the calculation.

Figure 11. Propagation of uncertainty

Table 6. Propagation of uncertainty of molar concentration of NaOH
Method

a (mL)

Sa

y (mol L-1)

Sy

Visual method

10.0

0.5

(10.00.5)

0.005

Statistical method

9.5

0.2

(9.50.2)

0.002

The unknown sample was analyzed with a conductometric titration using the NaOH,
previously standardized, as titrate. The Figure 12, and table 7, represent the calculation necessary
to know the concentration of vanillin in the sample, where cvanillin is the real concentration of
vanillin in the sample, VNaOH is the volume of NaOH used to reach the end-point, cNaOH is the
concentration of NaOH used as titrate and Vvanillin is the volume of the titrate.

Figure 12. Titration of vanillin by standardized NaOH

Table 7. Titration of vanillin by standardized NaOH

Method

cNaOH (mol L-1)

VNaOH (mL)

Vvanillin (mL)

cvanillin (mol L-1)

Visual method

(10.00.5)

(111)

50

(0.0230.002)

Statistical method

(9.50.2)

(10.70.1)

50

(0.02270.0002)

Once again, the propagation of uncertainty was analyzed, using the equation in the Figure
11, where a is the volume on the end-point, y is the concentration of vanillin and S is the
standard deviation of it respective subscript value; for the visual method, the standard deviation
of the volume was a half of the near increments volume (increments of 2 gives a deviation of
1.0), and the deviation for the statistical method was calculated using OriginPro 9.0. In the table
8 is shown the values used for the calculation.
Table 8. Propagation of uncertainty of molar concentration of vanillin
Method

a (mL)

Sa

y (mol L-1)

Sy

Visual method

11

0.023

0.002

Statistical method

10.7

0.1

0.0227

0.0002

With the molar concentration of vanillin it was possible to calculate the mass
concentration of this compound, using the Figure 13, and Table 9, where vanillin is the mass
concentration of vanillin (in g L-1), cvanillin is the molar concentration of vanillin (in mol L-1) and Mvanillin
is the molar mass of vanillin according to PubChem Database.

Figure 13. Mass concentration of vanillin

Table 9. Mass concentration of vanillin

Method

cvanillin (mol L-1)

Mvanillin (g mol-1)

vanillin (g L-1)

Visual method

(0.0230.002)

152.14732

(3.50.3)

Statistical method

(0.02270.0002)

152.14732

(3.450.03)

The uncertainty of this measure was calculated, using figure 11, where a is the molar
concentration of vanillin, y is the mass concentration of vanillin and S is the standard deviation
of it respective subscript value. In the table 10 is shown the values used for the calculation.
Table 10. Propagation of uncertainty of mass concentration of vanillin
Method

a (mol L-1)

Sa

y (g L-1)

Sy

Visual method

0.023

0.002

3.5

0.3

Statistical method

0.0227

0.0002

3.45

0.03

Conclusions

The standardization of NaOH was made and the graph describing the reaction with HCl
showed a trend similar to that the literature described, a V-shaped graph, with a minimum of the
curve representing the end-point of the reaction. The equivalence point was detected by visual
methods and statistical methods, with an equation proposed that represented the end-point as the
intercept between two straight lines. The concentrations calculated by this two methods were
(0.1000.005) mol L-1 and (0.1050.002) mol L-1, similar results that shows that the visual
method is a good approximation and that the equation proposed fits properly with what occur in
the reaction.
The conductance titration of vanillin showed a different behavior in comparison with the
standardization reaction of sodium hydroxide. This comportment was foreseen, since negativecharged ions are reactants in the acid-base reaction while on the reaction of vanillin with the
NaOH anions are the products, causing an increase in conductance of the reaction and changing
the shape of the graph; no inversion point was found and the visual method of analysis was
compromised.
However, with the mathematical transformations and the equation proposed, it was
possible to analyze and calculate the concentration of vanillin in the sample, (3.50.3) g L-1
using the visual method after first and second derivative, and (3.450.03) g L-1 with the
statistical approach.

References

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