Relative Contributions of IMF To Haloalkane Boiling Points (Pui Wah 2016)

Tang
Pui Wah Candidate Number: 0006380030
Chemistry Internal Assessment

Introduction

The internal assessment was started from an anomaly that I found when learning organic
chemistry. In this topic, we have to recall the microscopic properties, such as polarity, dipole
moment, electronegativity, Lewis structure etc., to explain the macroscopic physical trends in
homogenous series or reaction mechanism. When I came cross the trend in boiling point of
halogenalkane, the trend is contradicting the concept that I learnt on intermolecular forces.

Boiling point was known to be dependent on the intermolecular force between molecules which
included London dispersion forces, permanent dipole-‐dipole attraction and hydrogen bond. London
dispersion forces exist in both polar and non-‐polar molecules, it occurs between two opposite ends
of induce dipoles, which are formed when electron cloud is unevenly distributed at some instant.
Permanent dipole-‐dipole attraction only exists in polar molecules, attraction occurs between the
positively charged end of a molecule and the negatively charged end of another molecule. Last but
not least, hydrogen bond exists in molecule contains hydrogen boned with a very electronegative
atom, like oxygen, nitrogen, or fluorine, which would “pull” the electron pair from the hydrogen.

Hydrogen bond is known to be the strongest among those three intermolecular forces, following is
permanent dipole-‐dipole attraction and London dispersion force is the weakest. Halogenalkane is
mostly polar, and hydrogen is not boned with any oxygen, fluorine or nitrogen, so London
dispersion forces and permanent dipole-‐dipole attraction are the only intermolecular forces exist.
Since London dispersion force is weak, I believe permanent dipole-‐dipole attraction contributed
mostly to the boiling point. The strength of permanent dipole-‐dipole attraction depends on the
polarity of the molecule which is determined by the electronegativity difference. From the table,
the bond with with largest electronegativity difference is C-‐Cl, then is C-‐Br bond, and lastly C-‐I
bond.

Atom Electronegativity
C 2.5
Cl 3.0
Br 2.8
I 2.5
Figure.1 Electronegativity of carbon, chlorine, bromine, iodine

As the C-‐Cl should be the most polarized, the permanent dipole-‐dipole attraction should be the
strongest. Therefore, chloroalkane should have the highest boiling point, followed by the
bromoalkane and iodoalkane.

1
Tang Pui Wah Candidate Number: 0006380030
Boiling point of haloalkane with incaresing number of carbon

250
200
150
Boiling Point/℃
100
50
0
0 1 2 3 4 5 6 7 8 9 10
-‐50
-‐100
Number of Carbon
Chloroalkane Bromoalkane Iodoalkane

*Error bars are too small to be seen.

However, the result come out to be completely opposite. Iodoalkane tends to have higher boiling
point over bromoalkane and chloralkane. A possible explanation of that is the increase in molecular
mass contributes more to the boiling point than the polarity. To justify this hypothesis, I started
off with this Internal assessment with the research question: How much does the permanent
dipole-‐dipole attraction contributes to the boiling point of halogenalkane?

INVESTIGATION 1

Research Question:
How much does the permanent dipole-‐dipole attraction contribute to the boiling point of
halogenalkane?

Methodology:
Halogenalkane consists of London dispersion forces and permanent dipole-‐dipole attraction, while
alkane consists of London dispersion forces only. The strength of London dispersion forces is known
to be dependent on molar mass. Molecules with similar mass would have similar London force
between molecules, thus have similar boiling point. Therefore, by see how the boiling point of
halogenalkane differs from the boiling point of alkane with similar mass can reflect how much does
the permanent dipole-‐dipole attraction contribute to the boiling point of halogenalkane.
Dependent Variable:
The boiling point of haloalkane and alkane.
Independent Variable:
The molar mass of molecules.
Control Variable:
Only linear haloalkane/alkane was studied. 1-‐haloalkane were sampled to make it a fair comparison
as not every haloalkane has isomers with functional groups binding in carbon in the middle of the
molecule, but every haloalkane can exist in the form of 1-‐haloalkane which functional groups are
bonded at the end.

2
Data Collection:
Databases:
I. Chemspider
II. Chemistry Data Book 2nd edition in SI
Boiling points were collect on both Chemspider and Chemistry Data Book to increase the
creditability of the data. In investigation 1, the data was coherent, therefore an average value was
taken. Chemspider provide both experimental boiling point and predicted boiling point, in some
cases, the experimental boiling point was not available, the predicted boiling point was used, the
data would be specified for evaluation purpose.
Raw Data
Name Molar Mass Boiling Pt./℃ Resources Boiling Pt./ ℃ Resources
Methane 16 -‐164 ChemsS. -‐162 CDB
Ethane 30 -‐88 ChemsS. -‐88.6 CDB
Propane 44 -‐44.5 ChemsS. -‐42.2 CDB
Butane 58 0 ChemsS. -‐0.5 CDB
Pentane 72 36 ChemsS. 36.3 CDB
Hexane 86 69 ChemsS. 68.7 CDB
Heptane 100 98 ChemsS.
Octane 114 125 ChemsS.
Nonane 128 150-‐152 ChemsS.
Decane 142 172-‐174 ChemsS.
Undecane 156 196 ChemsS.
Dodecane 170 215-‐217 ChemsS.
Hexadecane 184 287 ChemsS.
Hexadecane 226 287 ChemsS.
Chloromethane 50 -‐24.2 ChemsS. -‐23.8 CDB
Chloroethane 65 12.3 ChemsS. 12.5 CDB
1-‐Chloropropane 79 46 ChemsS. 46.6 CDB
1-‐Chlorobutane 93 77-‐79 ChemsS. 78.5 CDB
1-‐Chloropentane 107 106-‐108 ChemsS. 108 CDB
1-‐Chlorohexane 121 132-‐134 ChemsS. 133 CDB
1-‐Chloroheptane 134 158.8 ChemsS.
1-‐chlorooctane 148 182-‐183 ChemsS.
1-‐chlorononane 162 201-‐202 ChemsS.
Bromomethane 95 3.56 ChemsS. 3.6 CDB
Bromoethane 109 37-‐39 ChemsS. 38.4 CDB
1-‐Bromopropane 123 70-‐71 ChemsS. 70.8 CDB
1-‐Bromobutane 137 101-‐102 ChemsS. 101 CDB
1-‐Bromopentane 151 127-‐129 ChemsS. 129 CDB
1-‐Bromohexane 165 154-‐158 ChemsS. 156 CDB
1-‐Bromoheptane 179 179-‐180 ChemsS.
1-‐Bromooctane 193 200-‐202 ChemsS.
1-‐Bromononane 207 200-‐201 ChemsS.
Iodomethane 142 41-‐43 ChemsS. 42.5 CDB
Iodoethane 156 70-‐73 ChemsS. 72.4 CDB
1-‐Iodopropane 170 101-‐102 ChemsS. 102 CDB
1-‐Iodobutane 184 129-‐131 ChemsS. 130 CDB
1-‐Iodopentane 198 154-‐156 ChemsS. 155 CDB
1-‐Iodohexane 212 179-‐181 ChemsS. 181 CDB
1-‐Iodoheptane 226 203-‐205 ChemsS.
1-‐Iodooctane 240 225-‐226 ChemsS.
1-‐iodononane 254 107-‐108 ChemsS.
3
Processed Data
Name Molar Mass/gmol-‐1 Avg. Boiling point/℃ Uncertainty/℃
Methane 16 -‐163 1.0
Ethane 30 -‐88.3 0.3
Propane 44 -‐43.35 1.2
Butane 58 -‐0.25 0.3
Pentane 72 36.15 0.1
Hexane 86 68.85 0.1
Heptane 100 98 0.3
Octane 114 125 0.3
Nonane 128 151 0.5
Decane 142 173 1.0
Undecane 156 196 1.0
Dodecane 170 216 1.0
Hexadecane 184 287 1.0
Hexadecane 226 287 1.0
Chloromethane 50 -‐24 0.2
Chloroethane 65 12.4 0.1
1-‐Chloropropane 79 46.3 0.3
1-‐Chlorobutane 93 78.5 1.0
1-‐Chloropentane 107 108 1.0
1-‐Chlorohexane 121 133 1.0
1-‐Chloroheptane 134 158.8 0.3
1-‐chlorooctane 148 181.5 0.5
1-‐chlorononane 162 201.5 0.5
Bromomethane 95 3.58 0.0
Bromoethane 109 38.4 0.0
1-‐Bromopropane 123 70.8 0.5
1-‐Bromobutane 137 101 0.5
1-‐Bromopentane 151 129 1.0
1-‐Bromohexane 165 156 2.0
1-‐Bromoheptane 179 179.5 0.5
1-‐Bromooctane 193 201.0 1.0
1-‐Bromononane 207 200.5 0.5
Iodomethane 142 42.5 1.5
Iodoethane 156 72.4 1.5
1-‐Iodopropane 170 102 0.5
1-‐Iodobutane 184 130 1.0
1-‐Iodopentane 198 155 1.0
1-‐Iodohexane 212 181 1.0
1-‐Iodoheptane 226 204 1.0
1-‐Iodooctane 240 225.5 0.5
1-‐iodononane 254 107.5 0.5

Calculation of uncertainty
Values of boiling point in ChemSpider are given both in exact values and range of value, while those
given in the Chemistry Data Booklet are all exact value. The uncertainty involved only exact value
would be calculated using average deviation which indicated by how much the average value differ
from the original values, the formula is given below;

4
Since all data given in the Chemistry Data Booklet fell in the range of values given in ChemSpider,
the value of boiling point in the Chemistry Data Booklet was directly used, and the uncertainty is
half of the range of value (See numbers in Red)
The uncertainty in molar mass is believed to be very minimal and insignificant. Therefore, the
values of molar mass are rounded up to integers which is precise enough in this investigation.

Analysis and Discussion:
Boiling point of halogenalkane and alkane with increasing molar mass
400
300
200
Boiling Point/℃
100
0
0 50 100 150 200 250 300
-‐100
-‐200
-‐300
Molar Mass/ gmol-‐1
Alkane Chloroalkane Bromoalkane Iodoalkane

By comparing the boiling points of the halogenalkane, the statistics is reasonable. Among the three
type of halogenalkane with similar mass, chloroalkane has the highest boiling point, bromoalkane is
the second highest and iodoalkane is the lowest. The result matches with my original thought that
the permanent dipole-‐dipole attraction is stronger in molecules with higher polarity, thus have
higher boiling point. However, the reasoning lost credibility once the boiling point of alkane is
added to the comparison.

Following the logic of my original thought, alkane only consist of London dispersion force while
halogenalkane consists of London force and a stronger intermolecular force-‐permanent dipole-‐
dipole attraction, so alkane should have lower boiling point than halogenalkane. The result come
out to go against this prediction, the boiling point of alkane is the highest among all. The boiling
points of alkane and chloroalkane are very close to each other, almost overlapping each other, it
justifies my hypothesis that the effect of permanent dipole-‐dipole attraction on boiling point of
halogen alkane is very small. Chloroalkane should have the strongest strength of permanent dipole-‐
dipole attraction, but addition of chlorine functional group does not seem to bring much effect to
the boiling point, so that we can assume the contribution of permanent dipole-‐dipole attraction to
the boiling point of bromoalkane and iodoalkane is trace, and thus ignorable.

An odd trend is observed here, although the effect of permanent dipole-‐dipole attraction was
proved to be minimal, the boiling point of bromoalkane and iodoalkane should not have lower
boiling point than alkane with similar mass, as they should have similar London dispersion force.
The anomaly tells us apart from molecular mass, something else is affect the strength of the
London dispersion force. To extend this topic further, a second investigation is carried out.
5
INVESTIGATION 2
Research Question:
How much do different physical properties of molecule account for the strength of London
dispersion force?

Background theory:
Before looking into what affects the strength of London dispersion force, we first need to know
what causes London dispersion force and why would it depend on molar mass. Non-‐polar molecule
has no dipole moment as their electrons are evenly distribution, take bromine as an example,
bromine exist in diatomic structure in nature, both atoms have 35 electrons, so the charge is
balanced out. However, when molecules collide with each other, electrons will repel electrons in
adjacent molecules, electrons will redistribute themselves to one side and cause a partially negative
charge and partially positive charge, this is how an instantaneous dipole is formed. Dispersion
forces or London forces as the weak attractive forces between molecules resulting from the small,
instantaneous dipoles that occur because of the varying positions of the electrons during their
motion about nuclei. Therefore the strength of London dispersion force rely on 2 factors:
I. Number of electrons:
An unsymmetrical distribution of a larger number of electrons will result in larger
instantaneous dipole.
II. Ease of dispersion of electrons:
Increasing ease of dispersion of electrons allows electrons to rearrange their position, thus
increase the ease to form instantaneous dipoles.
This is why molar mass is a parameter of the strength of London dispersion force. The above 2
factors increase with molecular size, since large number of electrons will make up large molecule
and electrons disperse easier in large molecules as they are far from the nucleus. In general,
molecular size and molar mass parallel one another. Therefore, we can say the strength of London
dispersion force increase with molar mass. However, in this case, halogenalkane and alkane with
similar mass differ a lot in size. In this investigation, the effect of different physical properties on
the strength of London dispersion force will be explored.

Dodecane(Mr:170 gmol-1) 1-Bromohexane(Mr:165 gmol-1) 1-Iodopropane(Mr:170 gmol-1)
Boiling Point: 216℃ Boiling Point: 156℃ Boiling Point: 102℃

6
Methodology:
London force is known to correlate with molecular size. The physical properties (molar mass, molar
volume and van der waals’ surface area) that related to molecular size are chosen to see how much
do they contribute to the boiling point. There are 2 type of surface area; Van der waals’ surface
area and solvent accessible surface area. Van der waals’ surface area is deduced from the atomic
radius; it can be described as the surface area of the molecule, while for the solvent accessible
surface area, it is the surface area that will contact with the solvent; it will vary with the size of
solvent molecule. Van der waals’ surface is used here, as the it serves the purpose of indicating the
distance between the electrons and the nucleus in 3-‐dimension. Excel solver is used to calculate the
proportion of effects on boiling point created by different physical properties.

Photo taken from: http://www.ccp4.ac.uk/html/areaimol.html

Procedure:
Input all data in an excel table. And a column for the predicted boiling point and input a function:
ax+by+cz. a, b and c is the variable to be solved by the solver, while x, y z is molar mass, surface
area and molar volume correspondingly. Add a column next to the predicted boiling point and
name it “Error” to store the square of the difference between the predicted boiling point and the
actual boiling point. Add a cell to calculate the sum of error. Use the excel solver function to change
the variables until the sum of error is minimum.

Since the increase of all three physical properties are supposed to result in a higher boiling point.
Variables a, b and c should be positive. However, some data points are negative, which may affect
the accuracy of the solving action. Therefore, I transform the value of boiling point form Celsius to
Kelvin.

Data Collection:
I. Chemspider
II. Chemistry Data Book 2nd edition in SI
III. Marvin Sketch
Boiling points were collect on both Chemspider and Chemistry Data Book to increase the
creditability of the data. Molar mass and molar volume are collected from Chemsipder. The van der
waals’ surface area is calculated in a molecular modelling software-‐Marvin Sketch.

7
Raw Data

Name Molar Mass Surface area Molar volume Avg. Boiling Avg. Boiling
-‐1
/gmol /Å / cm3 point/℃ point/K
Methane 16 58.17 N/A -‐163 110
Ethane 30 92.56 61.5 -‐88 185
Propane 44 123.83 78.1 -‐43 230
Butane 58 154.37 94.6 0 273
Pentane 72 184.93 111.1 36 309
Hexane 86 215.61 127.6 68 342
Heptane 100 246.04 144.1 98 371
Octane 114 276.73 160.6 125 398
Nonane 128 307.52 177.1 151 424
Decane 142 337.90 193.6 173 446
Chloromethane 50 74.36 56.4 -‐24 249
Chloroethane 65 107.41 72.9 12 285
1-‐Chloropropane 79 138.14 89.4 46 319
1-‐Chlorobutane 93 168.78 105.9 78 352
1-‐Chloropentane 107 199.34 122.5 108 381
1-‐Chlorohexane 121 229.85 139 133 406
1-‐Chloroheptane 134 260.43 155.5 158 432
1-‐chlorooctane 148 291.00 172 181 455
1-‐chlorononane 162 321.00 188.5 201 475
Bromomethane 95 78.56 58.2 3 277
Bromoethane 109 111.56 74.7 38 311
1-‐Bromopropane 123 142.33 91.2 70 344
1-‐Bromobutane 137 172.91 107.7 101 374
1-‐Bromopentane 151 203.47 124.3 129 402
1-‐Bromohexane 165 233.69 140.8 156 429
1-‐Bromoheptane 179 264.59 157.3 179 453
1-‐Bromooctane 193 295.11 173.8 201 474
1-‐Bromononane 207 325.83 190.3 200 474
Iodomethane 142 83.82 63.9 42 316
Iodoethane 156 117.01 80.4 72 345
1-‐Iodopropane 170 147.78 96.9 102 375
1-‐Iodobutane 184 178.32 113.4 130 403
1-‐Iodopentane 198 208.88 129.9 155 428
1-‐Iodohexane 212 239.04 146.4 181 454
1-‐Iodoheptane 226 270.00 162.9 204 477
1-‐Iodooctane 240 300.21 179.4 225 499
1-‐iodononane 254 331.23 195.9 245 518

Uncertainty
The uncertainty in molar mass is believed to be very minimal and insignificant. Therefore, the
values of molar mass are rounded up to integers which is precise enough in this investigation. The
uncertainty of the average boiling point is given in investigation 1. The uncertainty of the molar
volume is ±0.3 cm3
8
Analysis and Discussion:

*Screenshot of the excel table (J1,J2,J3 are the variables; J4is the objective cell)

Solver result
600
y = 1.2653x + 208.78
y = 1.2756x + 207.16
500
400
Boiling Point/℃
300
200
100
0
0 50 100 150 200 250 300
Molar mass/gmol-‐1
Actual b.p. Predicted b.p.

*Error bars are too small to be seen

Solver solution:
The minimum value of Error is 7208.3069, while a is 0.2560489 and b is -‐5.635578

𝐵𝑜𝑖𝑙𝑖𝑛𝑔 𝑃𝑜𝑖𝑛𝑡 = 0.26×𝑚𝑜𝑙𝑎𝑟 𝑚𝑎𝑠𝑠 − 5.65×𝑠𝑢𝑟𝑓𝑎𝑐𝑒 𝑎𝑟𝑒𝑎 + 12.0×𝑚𝑜𝑙𝑎𝑟 𝑣𝑜𝑙𝑢𝑚𝑒

Trend line equation of predicted boiling point: 𝑦 = 1.2653𝑥 + 208.78
Trend line equation of actual boiling point: 𝑦 = 1.2756𝑥 + 207.16

By looking at the 2 tend line equations of the predicted boiling point and actual boiling point and
the data points, we can tell the solver solution can accurately reflect how do different physical
properties count for the boiling point, provided that a sense of awareness of the uncertainties of
the molar mass, surface area, molar volume and boiling point are present.

The magnitude of the coefficient of the solver solution give an insight of which physical property
has a larger impact on the strength of London dispersion force/boiling point. Molar volume seems
to have the most significance on the boiling point, follow by surface area and lastly the molar mass.
9
This finding is reasonable, as the molar mass only account for the number of protons and electrons,
but it can not show the strength of attraction between them, where as the other 2 properties do,
due to the inclusion of the distance between the nucleus and the electrons. The coefficient of the
surface area is given as a negative number, which is not expected at first. It means that given the
molar mass and molar volume is constant, the larger the surface area the lower the boiling point.
This does not match with my hypothesis.

Molecules with large surface area should have large number of electrons and high ease of
dispersion of electrons, also, it provides a larger surface area for London dispersion force to take
place, which should result in a high boiling point. I tried to justify this claim by comparing the
boiling point of branched alkane and halogenalkane isomers, since the molecule share similar molar
volume and mass number, but the result seems to go against the claim, the boiling point tends to
decrease with the surface area. A possible explanation of that is the with the increase branching of
methyl group of alkane, the molar volume decrease, as molar volume is more impactful comparing
to surface area, so the drop of boiling point due to the decrease of molar volume are more
significant than the decrease of surface area.

Generally speaking, the molar volume and surface area are usually interconnected, an electron rich
molecule can form stronger instantaneous dipole-‐dipole attraction, since the electron distribution
will be more uneven than small molecule, also the electrons on the outer shell can be dispersed
more easily, as they are farther from the positive nucleus, thus the molecule is larger in size, and
hence the molar volume and surface area will both increase. And this explain the reason why these
two properties will have a larger impact on the boiling point.

Evaluation
1. Lack of data
Some data are not provided, such as the molar volume of methane, or the experimental boiling
point of 1-‐Chloroheptane, 1-‐iodononane etc. The predicted boiling point was used instead,
however the accuracy of the predicted boiling can not be justified. Therefore, the lack of data may
affect the accuracy of the prediction formula.

2.Selection of molecule
Only halogenalkane is studied in this investigation. Although boiling point of halogenalkane was
proved to be mostly contributed by the London dispersion force, permanent dipole-‐dipole
attraction did exist. To make my latter part of investigation more convincing, more molecule from
different homogenous group, like alkane, should be studied.

Also, only linear alkane and halogenalkane are sampled for the investigation, therefore although
the formula of predicted grade seems to fit the actual boiling point, it may not fit the other
molecules, like secondary, tertiary halogenalkane, well.

3.Uncertainty
In investigation 2, although the data points of the predicted boiling point are very close to the
actual boiling point. Some of the uncertainty was unavailable, and thus not taken into account, for
example the van der waals’ surface area of the molecules. The precision of the result may be
overestimated.

10
Conclusion:
The first part of the investigation discovers the fact that, although permanent dipole-‐dipole
attraction is a stronger intermolecular force than London dispersion force, the boiling point of
molecules consisting of permanent dipole-‐dipole attraction does not always have a higher boiling
point then non-‐polar molecules, especially in large molecules like halogenalkane. By grouping the
boiling boing of halogenalkene, the effect of permanent dipole-‐dipole attraction was found to be
trace, showing that London dispersion force is the dormant intermolecular force between the
molecules. This finding lead to the later part on the investigation on London dispersion force. The
impact of 3 physical properties: molar mass, surface area and molar volume on the strength of
London dispersion force is studied. Molar volume was found to be the most impactful, surface area
is the second and the molar mass is the least impactful. The result also suggests molecules with
similar molar volume or molar mass but larger surface area would have a lower boiling point.

Commenting on the precision of the result, seeing that the trends of boiling points coherent and
the uncertainty given in the data base is not significantly large, the precision of the result falls in an
acceptable range. Also, the high accuracy is justified by the close value between the predicted
boiling point and actual boiling point. To sum up, this model allows an accurate prediction of the
strength of London dispersion force of molecules.

Bibliography
"Intermolecular Forces: Explain Dispersion Forces." Intermolecular Forces: Explain Dispersion
Forces. N.p., n.d. Web. 16 Jan. 2016. <http://yeahchemistry.com/tutorials/intermolecular-‐forces-‐
explain-‐dispersion-‐forces>.

Chemspider. Royal Society of Chemistry 2015, n.d. Web. 15 Jan. 2016.
<http://www.chemspider.com>.

Marvin 15.12.14.0, 2015, ChemAxon, <http://www.chemaxon.com>.

Accessible Surface of a Molecule, Defined as the Locus of the Centre of a Solvent Molecule as It
Rolls over the Van Der Waals Surface of the Protein. N.d. AREAIMOL (CCP4: Supported Program).
Web. 15 Jan. 2016. <http://www.ccp4.ac.uk/html/areaimol.html>.

McGlashan, M. L., J. G. Stark, and H. G. Wallace. Chemistry Data Book. Second ed. London: John
Murray, 1982. Print.

11

Relative Contributions of IMF To Haloalkane Boiling Points (Pui Wah 2016)

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Relative Contributions of IMF To Haloalkane Boiling Points (Pui Wah 2016)

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Tang

Pui Wah Candidate Number: 0006380030

Chemistry Internal Assessment

Boiling point of haloalkane with incaresing number of carbon

Analysis and Discussion:

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