Experiment 1: Freezing Point Depression of Electrolytes

Physical Chemistry Laboratory

CHEM 445- 021L

Cristina Fernandez
Nathaly Murillo

Due Date: May 4, 2008

Submitted Date: May 4, 2008

Abstract
In this experiment the effect on freezing point depression relative to the

concentration of an electrolyte (HCl) was measured using a Dewar flask. It was found

that as the molality of HCl increases the freezing point of the solution decreases in a

linear fashion, meaning the freezing point depression increases with increasing molality.

The experimental data was shown to be consistently lower than that of an ideal

electrolyte. The equation fitting an ideal electrolyte is ΔTF= 3.72m, the experimental data

fits the equation ΔTF= 3.5336m. Osmotic coefficients and activity coefficients were

determines for these data. The osmotic coefficients did not follow any tangible pattern

but the activity coefficients were found to decrease with increasing molality. Last, using

the same methods as the experimental data, osmotic coefficients were calculated for a

given set of data for NaOH. The given data followed the trends of that of the

experimental data. The activity coefficients were measured in three different ways for the

given data set, first using the experimental equation, second using the DHLL equation

and third using the Debye-Hückel-Guggenheim equation. The results showed that the

first two ways of determining the activity coefficients are more accurate than the Debye-

Hückel-Guggenheim equation due to the inclusion of more parameters other than

molality.

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Introduction

Colligative properties are unique properties of solutions that depend only in the

solvent used and the concentration of the sample, in other words, they do not depend on

the chemical composition of the solution. The freezing point depression is one

colligative property greatly used. The freezing point depression for non-electrolytes is

described by the following equation:

ΔTF = Kf m (1)

In Equation (1), the freezing point depression constant, KF, for water is 1.860 °/molal and

m is the molality.

The osmotic coefficient, g, is the ratio of the experimental freezing point

depression of electrolytes solutions with the value of ideal strong electrolytes and it is

represented by the following equation:

(2)

The osmotic coefficient is less than 1 because the real electrolytes solutions do not

behave ideally due to the interionic forces. The osmotic coefficient depends on the

dilution; as the solution becomes more dilute , g approaches 1 as expressed by the

following equation:

Limit{g}m0 = 1 (3)

It is know theoretically that the osmotic coefficient is greatly affected by the ionic

charges as well as the ionic concentrations, and the equation that defines this relationship

is the ionic strength:

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 (4)

Also, the average activity coefficient of the electrolyte can be calculated using the

osmotic coefficient, g, at the temperature of the freezing solution. The equation to

calculate the average activity coefficient is the following:

(5)
Experimental Procedure

1. Freezing Point of Water:

The Dewar flask was filled half full with distilled water, and then ice until the

flaks was nearly full. The water and ice were stirred to ensure that the solution was mixed

well and also to prevent temperature gradients. Using a differential mercury thermometer

the freezing point of water was determined. The magnifying lens was used to read the

temperature with an accuracy of ± 0.00X°. The temperature was recorded three times

while the slurry was being stirred vigorously to obtain a constant value. This procedure

was repeated with another batch of distilled water and ice. The value for the freezing

point of water used in the proceeding calculations was the average of the recorded

temperature values.

2. Freezing Points of Solutions:

Approximately 5 mL of HCl were added to the water/ice slurry while being stirred

continuously until a constant temperature was obtained. The freezing point of the solution

was recorded three times (with an accuracy of ± 0.00X°), and then ~ 50 mL of aliquot

were removed and transfer to a labeled and weighed snap jar, with cap. The jar was

allowed to return to room temperature and then weighed.

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 The aliquot was then transferred to an Erlenmeyer flask to be titrated with NaOH

and calculate the exact amount of HCl in each solution. Once the amount of HCl in the

solution was found, one was able to back calculate to find the exact weight of the water.

This data were used to calculate the molality of HCl in the solution, mol{HCl}/Kg{H2O}.

The entire procedure was repeated to obtain the freezing point and concentrations of 10

solutions of HCl, keeping in mind that the freezing point depressions should had covered

a range from ~0.1 to 1°C. To avoid refilling the buret with NaOH during the titrations,

~25mL of aliquot were removed instead of 50mL as the concentration of HCl increased

due to the addition of ~5mL HCl.

Results and Discussion

Table 1a contains the data gathered during the experiment which consist of the

freezing points of each solution of HCl and their averages. Table 1b contains freezing

point depressions (ΔTf), the weight of each solution of HCl, the volume of the NaOH

solution used to titrate each HCl solution, the mmols of HCl titrated, and the molality of

each solution. Before the first recorded value of the freezing point of HCl, three values

were obtained but these were discarded due to a misunderstanding of the experimental

procedure. For the omitted values water and ice were added after every 50mL extraction

of the HCl solution which resulted in different freezing point temperatures due to dilution

of the solution and a temperature change due to the ice. These values were as follow:

5.000°C, 4.458°C, and 4.400°C. Another value was omitted between the first and second

recorded value due to a lack of indicator in the titrated solution. The freezing point for

this value was 4.355°C. Water and ice were added to solutions # 8 and # 9 since the

freezing point started rising instead of declining due to lack of ice and too little solution.

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This could have lead to some experimental error. For all solutions at least triplicate

freezing point values were obtained, but for some solutions more values were acquired

due to inconsistent temperature readings.

Figure 1 shows the linear relationship between the molality and the freezing point

depression of HCl for the data obtained experimentally, and also as it would appear if the

solution were an ideal electrolyte. It should be noted that the experimental freezing point

data is always lower than the ideal freezing point depression. This is due to interionic

interactions between the ions which are not taken into account in the equation for an ideal

electrolyte. To compensate for this, activity coefficients must be determined.

Table 2 contains the data used to calculate the osmotic coefficient, g. This was

calculated using Equation (2), which is the ratio between the experimental and ideal

values of the freezing point depression. It is a measure of the deviation between ideal and

real strong electrolytes. In an ideal solution, as the molality approaches 0, the osmotic

coefficient should reach 1. The value for solution # 1 was omitted since it yielded an

osmotic coefficient greater than one which may result in an activity coefficient greater

than one.

Figure 2 depicts the quadratic relationship between the osmotic coefficients of

HCl solution and the square root of the molality of the HCl solution. The square root of

the molality was used in order to fit the equation g= 1+ am1/2 + bm. The value for all

solutions was plotted first which lead to the following values: a=0.4051± 0.3234 and

b=-1.7214 ± 0.8538. Since the value for solution # 1 does not agree with our data, it was

omitted which lead to the following values of a and b: a=0.3628± 0.3884 and b= -1.5872

± 1.0696. This omission leads to better activity coefficient values.

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 In Table 3a the activity coefficients, γ, were calculated without solution #1. In

Table 3b the values for the activity coefficients in solution #1 were included. The

difference between the two is noted as Table 3b leads to activity coefficient values

greater than 1. Using the equation g= 1+ am1/2 + bm and Equation (5), an equation for the

activity coefficient was derived assuming that μ is equal to the molality of the solution

(m). The resulting equation is as follows:

Ln{γ} = 3am1/2 + 2bm (6)

Using the same concepts used for the HCl solutions, the osmotic coefficient and

the activity coefficients for the given set of data for NaOH in Table A were calculated.

These data are shown in Table 4. Also included are calculations for the activity

coefficients using the DHLL, Equations (7), and the Debye-Hückel-Guggenheim,

Equations (8):

(7)

(8)

The activity coefficients were first calculated using Equation (5) and g= 1+ am1/2 + bm.

The values for a and b were as follow: a=-0.3221±0.0420 and

b= 0.3019 ± 0.0532.

In Figure 3 the experimental values for the activity coefficients and those found

using Equation (7) and (8) were plotted against molality. These values are different from

each others since they take different elements into account. Equation (5) uses the osmotic

coefficient when calculating the activity coefficients. Equation (7) only uses the square

root of μ or the molality for 1,1 electrolytes in this case. Equation (8) takes the charge of

the ions and the ratio between the square root of μ and 1+μ1/2. Because Equation (7) only

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takes μ into account, it is not as accurate as the values obtained experimentally using

Equation (5) or Equation (8). Those values obtained using Equation (8) better represent

the experimental values.

Tables and Figures

Table 1a: Experimental Freezing Point Values of HCl Solutions.

Freezing Point of HCl Solution
Solution
#
1 2 3 4 5 6 7 8 9
Trial 1 4.413 4.355 4.318 4.270 4.240 4.200 4.165 4.130 4.120
Trial 2 4.413 4.355 4.318 4.270 4.245 4.200 4.165 4.150 4.120
Trial 3 4.413 4.355 4.318 4.270 4.245 4.200 4.165 4.205 4.120
Trial 4 4.245 4.155 4.115
Trial 5 4.150 4.115
Trial 6 4.145
Trial 7 4.145
Trial 8 4.145
Average
Freezing 4.413 4.355 4.318 4.270 4.244 4.200 4.165 4.153 4.118
Point

Table 1b: Primary Data for HCl Solutions.

Average
Weight
Solutio Freezing ΔTf Volume Molality
of mmol
n# Point of {expt'l} {NaOH} {HCl}
Solution HCl
Solution (ºC) (mL) (n/Kg)
(g)
(ºC)
1 4.413 0.155 49.7878 20.319 2.032 0.0409
2 4.355 0.213 24.9999 14.290 1.429 0.0573
3 4.318 0.250 25.0005 16.900 1.690 0.0678
4 4.270 0.298 24.9732 21.160 2.116 0.0850
5 4.244 0.324 24.9458 22.310 2.231 0.0897
6 4.200 0.368 24.9938 25.500 2.550 0.1024
7 4.165 0.403 24.9428 28.500 2.850 0.1147
8 4.153 0.415 24.6739 31.230 3.123 0.1271
9 4.118 0.450 28.6414 35.040 3.504 0.1229
• m = N{NaOH} = 0.1
• Relative Freezing Point of Water = 4.568 ºC
• Equations to calculate the molality of HCl:
o V{NaOH} (L) * m{NaOH}* (mol HCl/mol NaOH) = mol of HCl in
solution
o mol HCl* MW{HCl}= weight of HCl (g)
o Calculate the weight of the water :
 (Weight of solution)- (weight of HCl)= weight of water
o m{HCl} = mol{HCl}/Kg{H2O}

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 Table 2: Primary Data Used to Calculate the Osmotic Coefficient, g.
m
Solutio ΔTf ΔTf
n#
{HCl} m^(1/2) g{m}
(n/Kg) {calc.} {expt'l}
**1 0.0409 0.2022 0.152 0.155 1.018
2 0.0573 0.2393 0.213 0.213 0.999
3 0.0678 0.2603 0.252 0.250 0.991
4 0.0850 0.2915 0.316 0.298 0.942
5 0.0897 0.2995 0.334 0.324 0.971
6 0.1024 0.3200 0.381 0.368 0.966
7 0.1147 0.3387 0.427 0.403 0.944
8 0.1271 0.3566 0.473 0.415 0.877
9 0.1229 0.3505 0.457 0.450 0.984
** This data point was omitted in the following calculations because it is greater than 1
and it may result in activity coefficients greater that are greater than 1.
• For aqueous HCl solutions, ν = 2.

Table 3a: Activity Coefficients Obtained with one Data Point Omitted.
m ΔTf ΔTf Activity
Solutio
n#
{HCl} {calc.} {expt'l} g{m} Coefficient
(n/Kg) (ºC) (ºC) γ

**1 0.0409 0.152 0.155 1.018 N/A

2 0.0573 0.213 0.213 0.999 0.334
3 0.0678 0.252 0.250 0.991 0.304
4 0.0850 0.316 0.298 0.942 0.265
5 0.0897 0.334 0.324 0.971 0.256
6 0.1024 0.381 0.368 0.966 0.235
7 0.1147 0.427 0.403 0.944 0.217
8 0.1271 0.473 0.415 0.877 0.201
9 0.1229 0.457 0.450 0.984 0.206
**This data point was omitted because it yielded an activity coefficient greater than 1.
• Derived equation for activity coefficients:
Ln{γ} = 3am1/2 + 2bm (6)

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 Table 3b: Activity Coefficients Obtained using Solution # 1 Data. No Data Points
were Omitted.
m ΔTf ΔTf Activity
Solutio
n#
{HCl} {calc.} {expt'l} g{m} Coefficient
(n/Kg) (ºC) (ºC) γ

1 0.0409 0.152 0.155 1.018 1.111

2 0.0573 0.213 0.213 0.999 1.098
3 0.0678 0.252 0.250 0.991 1.087
4 0.0850 0.316 0.298 0.942 1.064
5 0.0897 0.334 0.324 0.971 1.057
6 0.1024 0.381 0.368 0.966 1.037
7 0.1147 0.427 0.403 0.944 1.017
8 0.1271 0.473 0.415 0.877 0.996
9 0.1229 0.457 0.450 0.984 1.003
• All the data were included and they yielded activity coefficients were greater than
1.
Table 4: Analysis of Literature Data for NaOH and Activity Coefficients using
Different Equations.
γ using γ using γ using
m{NaOH} ΔTf{expt'l} ΔTf{calc.}
m^(1/2) g{m} Equation Equatio Equation
(n/Kg) (ºC) (ºC)
(5) n (7) (8)
0.010 0.100 0.036 0.037 0.968 0.905 0.894 0.903
0.020 0.141 0.070 0.074 0.941 0.871 0.853 0.870
0.050 0.224 0.173 0.186 0.930 0.814 0.778 0.814
0.100 0.316 0.346 0.372 0.930 0.763 0.701 0.763
0.126 0.355 0.430 0.469 0.917 0.745 0.671 0.745
0.253 0.503 0.860 0.941 0.914 0.693 0.568 0.687
0.500 0.707 1.700 1.860 0.914 0.659 0.452 0.628
0.510 0.714 1.740 1.897 0.917 0.658 0.448 0.626
• Primary data obtained from Table A in lab manual.
• Equation that fits the data for g= 1+ am1/2 + bm is:
y=0.3019x2 – 0.3221x + 0.9937
• Derived equation for activity coefficients:
Ln{γ} = 3am1/2 + 2bm (6)

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Figure 1.

ΔTf {experimental}
ΔTf {calculated}
Linear ( ΔTf {experimental})
Freezing Point Depression of HCl (ΔTf ) vs. Molality of HCl Linear (ΔTf {calculated})

0.5
y = 3.72x
2
R =1
0.45

0.4
y = 3.5336x
2
0.35 R = 0.9891

0.3
ΔTf (°C)

0.25

0.2

0.15

0.1

0.05

0
0 0.02 0.04 0.06 0.08 0.1 0.12 0.14
molality (n/kgH2O)

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Figure 2.

Osmotic Coefficient of HCl vs. Square Root of Molality of HCl (mol/Kg of water)

1.400

1.200
2
y = -1.7214x + 0.4051x + 1.0005
2
R = 0.5716
1.000
osmotic coefficient {g}

with outlier value

0.800 without outlier value
Poly. (with outlier value)
Poly. (without outlier value)
0.600

2
y = -1.5872x + 0.3628x + 1
2
0.400 R = 0.4823

0.200

0.000
0 0.05 0.1 0.15 0.2 0.25 0.3 0.35 0.4
m^(1/2)

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Figure 3.

Osmotic Coefficient of NaOH vs. Square Root of Molality of NaOH

NaOH values

1 Poly. (NaOH
values)
0.99

0.98

0.97

0.96

0.95
g

2
y = 0.3386x - 0.3564x + 1
0.94 2
R = 0.9361

0.93

0.92

0.91

0.9
0 0.1 0.2 0.3 0.4 0.5 0.6 0.7 0.8
m^(1/2) (mol/kgH2O)

Conclusion

A linear relationship was found between the electrolyte concentration and the

freezing point depression. Because of ionic interactions between the molecules the

experimental data yields a consistently lower freezing point depression than if the

solution were ideal. The equation for an ideal electrolyte is: y= 3.72x, for the

experimental data the equation is: y= 3.5663x. Y being the freezing point depression and

x being the molality. The osmotic coefficient, or, the ratio between the experimental and

ideal values of the freezing point depression, measures the deviation between ideal and

real strong electrolytes. In an ideal solution, as the molality approaches 0, the osmotic

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coefficient should reach 1. There is no clear pattern to the degree of deviation in our data.

The calculation of the activity coefficients demonstrates a decrease of the activity

coefficients as the molality increases if the experimental equation is used to determine the

activity coefficients.

Using the same methods used to calculate the data obtained experimentally, a

given set of data for NaOH was calculated. For this set of data, a linear relationship

between freezing point depression and molality was found. The data for the osmotic

coefficient did not follow a tangible pattern either. For this set of data three different

ways to calculate the activity coefficients were used. Using the experimental equation,

the activity coefficients were also found to decrease as the molality increases. Using the

DHLL equation, the activity coefficients were found to decrease as molality increases,

just like with the experimental equation. These two ways of calculating activity

coefficients are the most alike since they take more than molality into account. The

Debye-Hückel-Guggenheim only takes into account molality, making this the most

deviant data.

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