RESULTS AND DISCUSSION

Table 1.1. Density measurements of the HCl solutions.

Molarity
0.005
0.010
0.015
0.020
0.025
H2O

Replicate

Mass of pycnometer, g

Mass of

, g/mL

Ave ,

empty

+ mixture

mixture, g

g/mL

13.7117

38.8540

25.1423

0.9795

0.99175

II

13.112

38.315

25.093

1.004

0.99175

13.7117

38.8319

25.1102

0.9782

0.9916

II
I
II

13.7117
14.136
16.136

38.8319
39.262
39.251

25.1102
25.126
25.115

1.005
0.9788
1.005

0.9916
0.9919
0.9919

13.953

39.553

25.6

0.99731

0.9975

II

13.112

38.033

24.921

0.9976

0.9975

13.420

38.847

25.427

0.9906

0.9985

II

13.197

38.335

25.138

1.0063

0.9985

13.953

39.547

25.594

0.9971

0.9971

II

13.112

38.02

24.908

0.9971

0.991

Using the mass of the empty pycnometer and the mass of the pycnometer with the liquid
mixture, the mass of the mixture itself can be attained. After obtaining the mass of the mixture,
the density of the mixture and its average was next. It can be observed that the average density
values of both trials in each molarity are very close to each other and were increasing. It is due to
their relationship which is directly proportional for basic substances but not in general. Higher
concentration means there is more mass of the solute and since solutes overall add negligible
increase in volume, the density will rise.

Table 1.2. Titration of the HCl solutions with standard 0.01M NaOH.

Parameter
Vol. aliquot,
mL
Mass aliquot,
g
VolNaoH
Final rdg,
mL
Initial rdg,
mL
Vol used, mL
MolHCl
In aliquot
Mass HCl, g
Actual
molality

Nominal molality of HCl solutions, m

0.010
0.015
0.020
I
I
I

0.025
I

10.00

10.00

10.00

10.00

9.795

9.781

9.788

9.9731

9.906

28.7

11.5

16.7

25.5

28.9

23

0.005
I
10.00

5.7

11.5

16.7

25.5

28.9

.000057

.000115

.000167

.000255

.000289

.00208

.00419

.00609

.009295

0.0105

.005821

.01176

0.017

0.0256

0.029

This table shows the values for the mass aliquot and the volume of the sodium hydroxide after
titration. The moles of HCl can then be calculated after and so are the values for the mass of HCl
o
and the actual molality. Actual molality will be used to determine the value of E g . It can be
observed that the actual molality also increases as the mass of HCl also increases. The actual
molality is just close to its molarity counterpart and is not exactly the same since the calculated
densities vary. The relationship of molarity, molality and density is as follows:
Since,
Molarity =

mol solute
Volume

(E1-1)

Density =

mass
Volume

(E1-2)

and

Rearranging the two equations (E1-1) and (E1-2) to obtain the Volume and equating the two will
result to
Volume = Volume

mol solute
mass
=
Molarity Density
mol solute Molarity
=
mass
Density

(E1-3)

But molality is mol solute / mass solvent, hence,

m=

Molarity
Density

(E1-4)

Therefore, the molality varies as the calculated density varies. In this experiment, titration was
used in order to obtain the mol of HCl present in each mixture. This must be the first possible
source of error noted. Since titration for each mixture was not performed by each group (i.e. only
one group has executed the titrations for all the mixtures), the calculated mol of HCl differ from
each other. Thus, the calculated molality is inaccurate.
A glass electrode is commonly used to obtain the emf of a certain solution. The pH electrode is
basically a galvanic cell. The glass membranes in glass electrodes are designed to allow partial
penetration by the analyte ion. For example, a hydrogen together with a reference electrode, commonly
the calomel electrode, serves to measure the actual hydrogen ion concentration of the solution. The
electrode maintains a constant potential at a given temperature.
The calomel electrode is a reference electrode based on the following redox reaction between Hg2Cl2 and
Hg:
Hg2Cl2(s) + 2e 2Hg(l) + 2Cl(aq)
The potential of a calomel electrode is determined by the activity of Cl in equilibrium with Hg and
Hg2Cl2. As shown in the Figure, in a saturated calomel electrode, the concentration of Cl is determined
by the solubility of KCl. The electrode consists of an inner tube packed with a paste of Hg, Hg 2Cl2, and
KCl, build within a second tube containing a saturated solution of KCl. A small hole connects the two
tubes and a porous wick serves as a salt bridge to the solution in which the saturated calomel electrode is
immersed. A stopper in the outer tube provides an opening for adding
addition saturated KCl. The short hand notation for this cell is

Hg(l) | Hg2Cl2(s), KCl(aq, sat'd) ||

The potential of a calomel electrode remains constant even there is a
loss of the solution to evaporation. This is because the concentration of
the Cl- is fixed by the solubility of KCl. The advantage of using this
electrode is that it can be used in any solution not being affected by
organic compounds. To perform a measurement at least some tiny
current must flow through across the glass electrode.

However, the values for the emf were calculated using the pH values obtained from a pH meter
since a glass electrode was not available. The values for emf were noted to increase as the
molarity increases.. This is because the emf is not only determined by a redox reaction but also
from the concentration of the reactants and products. The emf will decrease as the concentration
increases. This is because the emf depends on the nature of the concentration and the emf is a
measure of the spontaneity of a cell reaction, it is expected the voltage to fall.
Table 1.3. Measured emf and other calculated data for the HCl solutions.
Actual molality

emf, volts

Eo g

aH+

0.029
0.0256
0.017
0.01176
.005821

.32588
.31355
.25439
.2958
.278052

0.07156
0.07156
0.07156
0.07156
0.07156

0.00174
0.00319
0.04800
0.01386
0.05584

5.046 x 10-5
8.166 x 10-5
8.16 x 10-4
1.63 x 10-4
3.25 x 10-4

The activity coefficient of specie is a measure of the effectiveness with which that species influences an
equilibrium in which it is a participant. The activity coefficients were calculated using the E g and the
actual molality. The concentration of strong acids like HCl is based on the complete dissociation of H +. In
very dilute solution, where the ionic strength is minimal, this effectiveness becomes constant and the
activity coefficient becomes unity. Under such circumstances, the activity and the molar concentration are
identical (as are thermodynamic and concentration equilibrium constants). That is
[H+] = aH+

(E2-1)

Since HCl is also uniunivalent electrolyte solution, it follows that

a = (a+ a-)1/2

(E2-2)

where a is the mean activity

a+
m
+ =

- =

a
m

where + and - are the activity coefficients for the ions

(E2-3)

(E2-4)

 = (+ -)1/2

a+
a
m
= [
)( m )]1/2 =

a = m

a
m

(E2-5)

But since the concentration of HCl is only affected by the presence of H + ions (cations),
aH+ = a

(E2-6)

Using equations (E2-5) and (E2-6), it can be deduced that

aH+ = m

(E2-7)

Based from table 1.3, it can be observed that there are fluctuations in the values of emf. This inaccuracy
has led to discrepancies in the values of activity coefficient. This would be the result of the second
possible source of error the pH meter was not properly calibrated.

Throughout this experiment, there are several environmental influences played a big role on the
measured data as well as precision. This can be limited by sticking to lab procedures, but as long
as there is a human operator involved, they will never be eliminated. Aside from what stated
earlier, some sources of error include 1.) Using dirty glass.The glassware used in solution
preparation should be clean and free of chemical contamination to avoid a large effect on the
data and decreasing its accuracy. 2) The pH meter was not properly set to neutral pH.
Inconsistency in pH values would occur since the pH meter might contaminate the solution
which will be passed to other group.

3.) Inaccurate dilution of HCl solution affects its

concentration and hence, affects the calculated emf. 4.) Overtitration might lower the
concentration 5.) Buret was not fixed vertically during titration which led to misreading of
meniscus.

CALCULATIONS:
TABLE 1.1 Density measurements of the HCl solutions.
@0.005
Mass of mixture: 38.8540-13.7177= 25.1423
mixture = ( mass mixture/mass water) P water
= (25.1423/25.594)(0.997075)
=0.9795 g/mL
@0.010
Mass of mixture: 38.8219-13.7177= 25.1102
mixture = ( mass mixture/mass water) P water
= (25.1102/25.594)(0.997075)
=0.9782 g/mL
@0.015
Mass of mixture: 39.262-14.136= 25.126
mixture = ( mass mixture/mass water) P water
= (25.126/25.594)(0.997075)
=0.9788 g/mL
@0.020
Mass of mixture: 39.553-13.953= 25.6
mixture = ( mass mixture/mass water) P water
= (25.6/25.594)(0.997075)
=0.99731 g/mL

@ 0.025
Mass of mixture: 38.847-13.420= 25.427
mixture = ( mass mixture/mass water) P water
= (25.427/25.594)(0.997075)
=0.9906 g/mL
@ H2O
Mass of mixture: 39.547-13.953= 25.594
Table 1.2. Titration of the HCl solutions with standard 0.01M NaOH.
@ 0.005
MOLES HCl = (0.010 M NAOH) (L NAOH)
= (0.010 M NAOH) (5.7/100) = 5.7 x 10-5 mol
MASS OF HCl= (moles of HCl) (MM HCl)
= (5.7 x 10-5) (36.453) = 2.08 x 10-3 g
ACTUAL MOLALITY = (mol HCl)/(mass aliquot-mass of HCl)
= (5.7 x 10-5)/ [(9.795-2.08 x 10-3)/1000]
= 5.82 x 10-3 m
@ 0.010
MOLES HCl = (0.010 M NAOH) (L NAOH)
= (0.010 M NAOH) (11.5/100) = 1.15 x 10-4 mol
MASS OF HCl= (moles of HCl) (MM HCl)
= (1.15 x 10-4) (36.453) = 4.19 x 10-3 g
ACTUAL MOLALITY = (mol HCl)/(mass aliquot-mass of HCl)
= (1.15 x 10-4)/ [(9.781-4.19 x 10-3)/1000]
= 1.176 x 10-2 m

@ 0.015
MOLES HCl = (0.010 M NAOH) (L NAOH)
= (0.010 M NAOH) (16.7/100) = 1.67 x 10-4 mol
MASS OF HCl= (moles of HCl) (MM HCl)
= (1.67 x 10-4) (36.453) = 6.09 x 10-3 g
ACTUAL MOLALITY = (mol HCl)/(mass aliquot-mass of HCl)
= (1.67 x 10-4)/ [(9.788-6.09 x 10-3)/1000]
= 0.017 m
@ 0.020
MOLES HCl = (0.010 M NAOH) (L NAOH)
= (0.010 M NAOH) (25.5/100) = 2.55 x 10-4 mol
MASS OF HCl= (moles of HCl) (MM HCl)
= (2.55 x 10-4) (36.453) = 9.2955 x 10-3 g
ACTUAL MOLALITY = (mol HCl)/(mass aliquot-mass of HCl)
= (2.55 x 10-4)/ [(9.9731-9.2955 x 10-3)/1000]
= 0.0256 m
@ 0.025
MOLES HCl = (0.010 M NAOH) (L NAOH)
= (0.010 M NAOH) (28.9/100) = 2.89 x 10-4 mol
MASS OF HCl= (moles of HCl) (MM HCl)
= (2.89 x 10-4) (36.453) = 0.0105 g
ACTUAL MOLALITY = (mol HCl)/(mass aliquot-mass of HCl)
= (2.89 x 10-4)/ [(9.906-0.0105)/1000]
= 0.029 m

TABLE 1.3 Measured emf and other calculated data for the HCl solutions.
MV = (7.0 Measured Ph) * 59.16

E Eg0 0.0592log 0.0592log m

@ 0.025
MV = (7.0 1.5) * 59.16 = 325.38
Emf, Volts = .32538
.32538= 0.07156 0.0592 log

0.0592 log 0.029

= 0.00174
aH+= (0.029)( 0.00174) = 5.046 x 10-5 m
@ 0.020
MV = (7.0 1.7) * 59.16 = 313.55
Emf, Volts = .31355
.31355=0.07156 0.0592 log

0.0592 log 0.0256

= 0.00319
aH+= (0.0256)( 0.00319) = 8.166 x 10-5 m
@ 0.015
MV = (7.0 2.7) * 59.16 = 254.39
Emf, Volts = .25439
.25439=0.07156 0.0592 log

0.0592 log 0.017

= 0.04800
aH+= (0.017)( 0.04800) = 8.16 x 10-4 m

@ 0.010
MV = (7.0 2.0) * 59.16 = 295.8
Emf, Volts = .2958
.2958= 0.07156 0.0592 log

0.0592 log 1.176 x 10-2

= 0.01386
a

= (1.176 x 10-2)( 0.01386) = 1.63 x 10-4 m

H+

@ 0.005
MV = (7.0 2.3) * 59.16 = 278.052
Emf, Volts = .278052
.278052=0.07156 0.0592 log

0.0592 log 0.005821

= 0.05584
aH+= (0.005821)( 0.05584) = 3.25 x 10-4 m

CONCLUSION AND RECOMMENDATIONS

The entire experiment primarily focused on determining the activity and activity coefficient
using cell emf. Initially, the emf should be obtained through the use of a pH meter with an mV
scale however, due to the unavailability of this particular apparatus, we tend to use a normal pH
meter. The pH values attained were used to calculate the emf. The pH meter was suspected to be
inappropriately calibrated and not consistent at all. All throughout the experiment, designated
mixtures were prepared by each group and these mixtures were passed from one group to
another. Improper dilution of HCl solution and cross contamination due to not calibrated pH
meter result to inconsistency in the pH values obtained by each group. Although there are little
fluctuations in the calculated values for activity and activity coefficients, this can still be
considered as precise since they follow the relationship: emf increases as concentration
increases. Here are some suggestions in performing this experiment: First of all, the preparation
of diluted HCl solutions should be done by a particular group in order to have consistency in
measurements. Secondly, if the pH meter with mV scale would not be available, properly
calibrated pH meter should be provided. Finally, the titration process must be done by each
group as much as possible in order to obtain uniformity in data. The buret should be line up
properly with the meniscus of the liquid being measured to get the accurate measure.
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