Chemistry Internal Assessment

Research Question: Do chain lengths effect the

Melting and boiling point of Esters and their aroma?
Candidate Number: 0002
Centre Number: 000981
Subject: Chemistry (group 6)
Session: May 2018
1 Introduction
1.1 Introduction

Having spent the majority of my life near Thailand’s largest industrial zone and
world 8th largest petrochemical industrial Hub I am no stranger to the wonders
of what we can turn hydrocarbons into, whether it’s fuel, plastics, paints or
perfumes. And upon learning about the process of esterification in chemistry
and how by simply refluxing an acid and alcohol we are able to create our own
perfume (with many toxic impurities). And upon further investigation into esters
I’ve discovered that they have very high boiling points points which made me
wonder if there is any correlation between the chain length on the alcohol part
of the ester, the chain length on the acid part of the ester or both to the melting
point and boiling point of the ester, and does this impact the aroma of the ester
at all. As I am also a biologist learning about esters can be crucial for me in the
future because I may need to synthesise or analyse different properties of
esters, which are found in the form of triesters, e.g. triglycerides.
1.2 Research question
I. Research Question: Do chain lengths effect the Melting and boiling
point of Esters their aroma, and if so is there a trend for possible
deduction?
II. how much ester can be produced in a period of 50 minutes when
varying the chain length of the components?
1.3 Hypothesis
iI believe that the chain length of both the Alcohol and the acid parts of the ester
effects the melting and boiling point equally the longer the chain length the
higher the boiling points due to increasing van der Waals dispersion forces
between the molecules, additionally the ester molecules I will be exploring are
all straight chain with the exception of Methyl benzoate, therefore temporary
dipole moment created the mobile electrons within the molecule being at one
side of the atom more than the other due to their random movement. The
temporary dipole sets up an induced dipoles in molecules next to it if they are
less polar, but becomes induced dipole if they are more polar. And due to the
increased surface area of a straight
chain molecule there will be more
temporary dipoles. The trends here
can be seen on the graph towards
the right.
It is important to note that the
melting point and boiling point
discussed in this hypothesis are
expected to be relatively higher or
lower than the other esters that will Diagram 1
be mentioned. Furthermore, there should be a method to predict what the
melting and boiling point is as the rate change should be constant as you add
more carbon. I expect this to happen because we are adding a constant amount
of electrons to the molecule with each CH2, therefore there should also be a
fixed increase in the intermolecular forces. And that more esters will be
produced with shorter chains. As intermolecular forces also increase as the
chain length within the carboxylic acid increases, additionally, because similar
to alcohols carboxylic acid has stronger van der Waals dispersion forces as
chain length increases and can form dipole-dipole bonds and hydrogen bonds
therefore stronger intermolecular forces, however carboxylic acid can also form
2 hydrogen bonds between 2 molecules to produce a dimer (Clark, 2015)
doubling the size of the molecule and the van der Waals dispersion forces. All
this means that the longer the chain lengths involved in the ester the longer it
will take for the reaction to initiate. Eg in the diagram below the hydrogen bonds
have to be broken first before esterification.

ii

Diagram 2

2 Methodology
2.1 Methodology
Firstly, I planned to undergo the esterification process following the Fischer
esterification mechanism (organic chemistry portal, n.d.) of methanol and
salicylic acid to form methyl salicylate under the same temperature setting on
the heating mantle and 0.1 Moles of acid and 50cm 3 of alcohol, the alcohol will
be varied between methanol, ethanol and propanol and the acid salicylic,
benzoic and ethanoic acid, each acid and alcohol variation was to be repeated
3 times. The general esterification equation for methyl salicylate is shown
below, intermediates are not shown.

iii

Diagram 3

The product was to be distilled until all the ester has evaporated and condensed
in the collection vessel. Side products or intermediates that may persist in
solution are disregarded as it is too difficult to separate. However, very early on
in the experiment I encountered a major problem where methyl salicylate when
left to cool undergoes a reverse reaction and converts back to salicylic acid.
Also when trying to extract the methyl Benzoate using distillation which releases
a lot of toxic methanol I decided to not do the practical because of the health
and concern issue which included: working with toxic low melting point alcohol
such as methanol (medscape, 2017) without proper ventilation and a respirator,
the use of highly concentrated H2SO4 acid as a catalyst and working with highly
volatile and flammable substances whilst other students are burning food and
the lack of proper equipment such as a respirator, reflux column etc., also
considered performing the Baeyer-Villiger oxidation method of esterification
however we do not have any ketones or lactones to oxidise with peroxide
illustrated in the diagram below (diagram 4) and as I’ve read (Seymour, 2013)
that highly toxic unwanted side products such as epoxides (diagram 5) can be
produced so I decided to not proceed with this method, Although it would’ve
been an interesting practical.

Diagram 4 iv

v
Diagram 5

I now plan to use the average melting and boiling points from 3 different
databases to conduct my exploration.
The alcohol variants are: Methanol, Ethanol, Propanol, Butanol and pentanol.
The acid variants are: Methanoic (formic) acid, Ethanoic acid, Propanoic acid,
Butanoic acid, pentanoic acid and benzoic acid.
The databases I will be using is Alfa Aeser, Chem expert and Lab networks.

2.2 Apparatus:
- Distillation apparatus for distillation and refluxing
- 100cm3 Round bottom flask
- top pan balance 2.d.p
- spatula
- databases x3
3 Processed Results from database
3.1 Table, Fixed Alcohol chain length and varying carboxylic acid
chain length’s Melting and boiling points
Ester Structure of ester Average Average
Melting point Boiling point
(oC) (letters are (oC) (letters are
database codes key below) database codes key below)

(1C) Methyl -100.0 32.3

methanoate C/A C/A/L
(2C) Methyl -98.0 57.3
ethanoate C/A/L C/A/L

(3C) Methyl -88.0 78.8

propanoate C/A/L C/A/L

(4C) Methyl -84.5 101.8

butanoate A/L C/A/L

(5C) Methyl -91.0 126.5

pentanoate A C/A

(7C) Methyl -12.0 198.5

benzoate A/L A/L

Table 3.2 Fixed carboxylic acid chain length and varying alcohol
chain length’s Melting and boiling points
Ester Structure of ester Average Average
Melting point Boiling point
(oC) (letters are (oC) (letters are
database codes key database codes key
below) below)

(1C) Methyl -100.0 32.3

methanoate C/A C/A/L
(2C) Ethyl -80.5 53.8
methanoate C/A/L C/A/L
 (3C) Propyl -93.0 80.7
methanoate C/A/L C/A/L
(4C) Butyl -91.3 107.0
methanoate C/A/L C/A/L
(5C) Pentyl -73.5 125.0
methanoate A/L A/L

Key:
A - Alfa Aeser
C - Chem expert
L - Lab networks.
3.3 Graphs for Melting point and boiling points of a fixed alcohol and
varied carboxylic acid

Average Melting point (oC) Average Boiling point (oC)

250
0
200
-20 150
100
-40
50
-60 0

-80

-100

-120

3.4 Graphs for Melting point and boiling points of a varied alcohol
and fixed carboxylic acid
Average Boiling point (oC)
o
Average Melting point ( C)
140
0 120
100
-20 80
60
-40 40
20
0
-60

-80

-100

-120

4. Analysis
4.1 Analysis of Table 3.1-2 (Structure /melting and point tables)
With Regards to Table 3.1 it is clearly evident that the boiling point increases
down the table as the structure of the carboxylic acid is more complex, and the
chain length increases with an average increase of around 23.6oC (3.s.f) as the
chain length increases by one carbon. With the exception of the 7 carbon
carboxylic chain (benzoic acid) where the difference in boiling temperature from
the 5 carbon carboxylic acid ester is 72 oC or if we were to consider the 6
carbon acid which is not in the table, with the assumption that the 6 carbon acid
is 23.6 oC above the 5 carbon, the difference between the 6 carbon acid and 7
carbon acid will be 48.4 oC which is around double the average increase rate.
When considering the Melting point, we can also see a similar trend where the
longer the chain length the higher the melting point, with an anomaly of the 5
carbon acid molecule (Methyl pentanoate) who’s melting point decreased from
the melting point of the 4 carbon acid ester.

With regards to Table 3.2 it is also clearly evident that the boiling point of the
ester increases down the table as the structure of the carboxylic acid gets more
complex, and the chain length increases with an average of 23.2 oC (3.s.f).
When considering the melting point shown in this table we can also see a
similar trend where the longer the chain length the higher the melting point, with
an anomaly of the 3 carbon alcohol molecule (Propyl Methanoate) who’s
melting point decreased from the melting point of the 2 carbon alcohol ester.
4.2 Analysis of graphs 3.3-4 (melting and boiling point comparison
between different chain lengths /graphical representation of the data
in tables 3.1-2)
With regards to graphs 3.3 there is a steady increase in the boiling point as the
chain length of the carboxylic acid end of the ester increases, whilst with
regards to the melting point there is no steady increase as the rate fluctuates
and at the 5 carbon carboxylic acid the melting point decreases from the 4
carbon, there is also a massive increase between the 5 carbon and the 7
carbon carboxylic acid.
With regards to graphs 3.4 there is a steady increase in the boiling point as the
chain length of the alcohol end of the ester increases, whilst with regards to the
melting point there is a steady increase with the exception of Ethyl methanoate
who’s melting point is higher than what was to be expected.

5 Discussion, Conclusion and Evaluation

5.1 Discussion of analysed data

With regards to the data collected, processed and analysed it is absolutely clear
that there are similar trends in the melting and boiling points of esters in the
carboxylic acid and the alcohol both averaging increase1 at around 23oC per
more carbon added to the chains therefore confirming my hypothesis that
longer chain length in both components of the esters will increase their boiling
points equally, this is to be expected because when looking at just Methane and
Ethane, there is a massive increase between the boiling point due to increase in
London dispersion forces between the carbons, the more carbons the more
London dispersion forces (Z, 2014) as there is a greater relative surface area
for the delocalised mobile electron to form a stronger temporary dipole. The
same should be expected from adding more Carbons (increasing chain length)
to both the alcohol and carboxylic acid as they are essentially an alkane with an
addition of the functional group Hydroxyl or Carboxyl.
I am confident that for a rough estimate of the boiling point of any chain
length of an ester, provided that a value is known for one ester, one must simply
add 23 oC for every extra carbon in the molecule, this partially confirms my
hypothesis that it is possible to find a trend for the prediction of the boiling point
of an ester. However, after looking at the trends above I decided to make a
model for prediction of the boiling point2. Every number here has to be at 5.d.p
for the functions to be accurate. Let x = Chain length
For fixed methanol and Varied carboxylic acid (Diagram 6 shows best fit line
and actual data):
𝑓(𝑥) = 10.73463 + 22.18714𝑥 + 0.18621𝑥²
For fixed Methanoic (formic) acid and varied alcohol(Diagram 6 shows best fit
line and actual data):
𝑓(𝑥) = 9.33607 + 22.69027𝑥 + 0.21348𝑥²
Under the constraints mentioned above the function should be valid at least up
to 15 Carbon (chain length). Random trial using these two function using a
chain length of & carbon returned an accuracy of approximately  3.5 oC.

Diagram 6 Diagram 7

It is also noticeable where the Methyl Benzoate had a considerably higher

boiling point then the others this due to the Benzene ring in the benzoic acid.

1Averages calculated using AVERAGE function on excel

2Boiling points were graphed in GeoGebra in the y-axis and chain length in the x-axis, I
calibrated the function by doing 32.3 (chain length of 1 carbon BP) +15(average
change) to get the 15 chain length Boiling point.
Benzene rings have been known to have a high boiling point for a hydrocarbon
because of van der Waals dispersion forces between neighbouring molecules
(chemguide UK, 2016) . Methyl Benzoate not only like benzene rings have van
der Waals dispersion forces, they also have a permanent dipole like
Methylbenzene meaning that dipole-dipole attraction will also contribute to the
high boiling point. This permanent dipole is created when delocalised mobile
electrons in the pi-orbitals of the benzene ring is attracted and moves closer to
the highly electronegative Oxygen atom of the ester.
When considering the melting point however, both chain length for
carboxylic acid and alcohol show similar trends where the rate of change
between interval carbons differs and no real trend can be created that will
provide a method of predicting the melting point of an ester, this was
unexpected because I thought that London dispersion forces between the
carbons within the ester will increase as the chain length increases thus the
melting point should show a similar trend as as London dispersion forces
increases there should also be increase attraction between each hydrocarbon
molecule. However, there is a possible explanation for this; in order for
intermolecular forces to act efficiently in solids the molecules must be closely
packed together in a lattice for the strongest intermolecular attraction, however
the C-O-C bond of the ester has a low rotational energy barrier therefore the
molecule is flexible and less rigid which causes a low melting point throughout.
(lumenlearning.com, 2017) Thus disproving my hypothesis where I believed that
there is a constant trend in the melting point.
Furthermore, addressing the other part of my hypothesis regarding the
aroma of the esters I have no definitive proof to confirm my hypothesis as I do
not have access to these esters to provide a qualitative analysis, after multiple
failed attempts at synthesising then some and health and safety concerns
explained earlier convinced me not to proceed. However, under the assumption
that the aromatic quality of the ester is due to its high volatility I believe that
shorter chain lengths will mean that the ester will have a stronger aroma as
shorter chain lengths means weaker forces of attraction between the molecules
therefore shorter esters are more volatile, and the molecules are more readily
available to overcome the intermolecular forces and evaporates.

5.2 Conclusion
To conclude, my hypothesis was partly correct, there is an equally strong
increasing trend between boiling points and increasing chain lengths of the
different components of an ester due to increasing van der Waals dispersion
forces because of the greater surface area of larger molecules allowing for
stronger temporary dipoles and induced dipoles. However, there is a very weak
trend for melting points due to the high flexibility and ability to rotate of the C-O-
C bond (March, 1992). I was unable to find any evidence to support my
hypothesis that shorter chain length equates to more ester being produced in
the same amount of time as longer chain length alcohol or carboxylic acid used
in esterification due to lack of proper apparatus and health and safety concerns
described earlier. Despite this I still feel strongly that the theory I have
mentioned in my hypothesis will hold through.

5.3 Evaluation
My Impression of this exploration is that it turned out pretty well and I have
enjoyed researching and writing this paper. The strength of my research is due
to using a database, I felt like I have used data from experiments that have
been repeated more times than I could’ve done by myself, moreover, the
apparatus used by these labs are far more appropriate and sophisticated than
what I had access too, and the samples used were far purer than what I
could’ve achieved. However, there are some room for errors that I have to be
address, due to various health and safety concerns, I had no other option but to
rely on the database portion of my exploration alone, this means that I have no
access to how these figures were obtained therefore if there was any errors in
my exploration with regards to these figures versus actual experimental data I
will have to assume it is due to uncertain propagation rather than a systematic
error as any and all equipment and apparatus used to determine these figures
should be very precise and accurate. Furthermore, some databases did not
have the information for all the esters in my experiments therefore some
averages are of 2 or 1 database(s) instead of 3, this is also problematic
because other databases weren’t open to the public I was only able to find 3
databases for comparison which may have hindered how accurate my average
was. I was also unable to do any meaningful practical due to time constraints
and lack of apparatus. If I was to revisit this research in the future I would most
definitely use more than three databases to for a more reliable average to use, I
would also like to have the proper apparatus such as a reflux kit and proper
distillation apparatus and a working fume hood to prevent any methanol toxicity,
Moreover, to prevent incidents where the ester’s equilibrium seemingly favour
the left side of the reaction after being left to cool I will use a lot more alcohol
than 50cm3, fractional distil out the ester after neutralising the acid catalyst
using NaOH and drying the solution using a molecular sieve or drying agents,
then I would run the sample through gas chromatography to find the purity of
the sample and then use a temperature probe and heat source to record the
temperature change, to identify the boiling plateau, repeats are done using
chemicals from the same set for minimum discrepancies between samples, I
would also like to have samples of all the esters I have listed to gather some
qualitative data of their aromas. Lastly I would also like to synthesise esters
using the Baeyer-Villiger oxidation method mentioned in my Methodology
section as then I can compare the relative efficiency between the fischer-
esterification and this method.
Appendix
Raw Data tables

Bibliography
Clark, J. (2015). Retrieved 3 6, 2018, from
https://www.chemguide.co.uk/organicprops/acids/background.html
labnetwork. (n.d.). Retrieved from https://labnetwork.com.cn/
chemguide UK. (2016, 2). Retrieved 2018, from
https://www.chemguide.co.uk/organicprops/arenes/background.html
chemspider. (n.d.). Retrieved from http://www.chemspider.com
lumenlearning.com. (2017). Retrieved 03 23, 2018, from
https://courses.lumenlearning.com/introchem/chapter/esters/
Alfa Aesar. (2017). Retrieved 2018, from https://www.alfa.com/en/structure-search
March, J. (1992). Advanced Organic Chemistry (4th Edition ed.). New York, New York,
USA: Wiley & Sons.
medscape. (2017, 1 30). Retrieved 3 6, 2018, from
https://emedicine.medscape.com/article/1174890-overview
organic chemistry portal. (n.d.). Retrieved 2018, from http://www.organic-
chemistry.org/namedreactions/fischer-esterification.shtm
Seymour, C. (2013, 7 16). Online. Retrieved 3 6, 2018, from
http://www.scs.illinois.edu/denmark/wp-content/uploads/gp/2013/gm-2013-
7-16.pdf
Z, E. (2014, aug 28). Retrieved 2018, from https://socratic.org/questions/why-do-van-
der-waals-forces-increase-with-the-size-of-molecules

i Diagram 1 from http://chemistry-reference.com/alkanes/default.asp

ii Diagram 2 from http://www.chem.ucla.edu/~harding/IGOC/D/dimer.html

iii
Diagram 3 from http://www1.biologie.uni-hamburg.de/b-
online/library/newton/Chy251_253/Lectures/Esterification/Esterification.html

iv Diagram from https://en.wikipedia.org/wiki/Baeyer%E2%80%93Villiger_oxidation

v Diagram from https://en.wikipedia.org/wiki/Epoxide