Experiment no.

2
Melting Point Determination
(Prelab Discussion)
Physical Property

• Any property of a substance that can be observed without transforming

the substance into some other substance

melting point
Physical Property

• In studying organic compounds, the following are the common physical

properties that are being measured:

Physical
Properties

Melting Point Boiling Point Solubility

Melting Point

• Temperature at which a given solid material changes from a solid state to a

liquid, or melts.

• Dependent on the intermolecular forces of attraction between the solid

particles and the packing of the crystal structure

solid liquid
Melting Point Determination

Melting points are determined for three reasons:

1. If a compound is a known one, the melting point will help to characterize
the sample.
2. If the compound is new, then the melting point is recorded to allow
future characterization by others.
3. The range of the melting point is indicative of purity of the compound –
an impure compound will melt over a wide range of temperatures
Objectives

• To assemble the proper setup for melting point determination

• To perform and determine melting point of different organic substances.

• Determine purity of organic substances by comparing the results obtained

between samples and between the actual and theoretical values.

• To explain the effect of structure of compound to its melting point

Procedure

A. Rough Method
1. Research on the theoretical melting point of naphthalene and benzoic acid to
be used as a guide in actual determination of the melting point.

2. Using a Bunsen burner, prepare 3 capillary tubes by sealing one end.

3. Pulverize each naphthalene and benzoic acid separately using a mortar and
pestle and form a heap of each sample.

4. Introduce each sample gradually into the capillary tube occupying 1 cm of the
capillary tube.
Procedure

5. On the 3rd capillary tube, add a mixture of naphthalene and benzoic acid in a
1:1 ratio occupying 2 cm of the capillary tube.

6. Attach the capillary tubes with the samples to the thermometer using a ring of
rubber tubing. The capillary tube should be attached in a manner that the solid
sample inside the capillary tube is alongside the bulb of the thermometer.

7. Immerse the thermometer with the capillary tube in the mineral oil bath and
heat the bath.

8. Record the temperature range at which the pure substance and the mixture
begins to liquefy until it has completely liquified. Note any sintering, coloring,
softening or any signs of decomposition.
Procedure

Thiele tube set-up

Procedure
Procedure

sample before melting sample starts to melt sample melts completely

Results

THEORETICAL: 80.26 °C
THEORETICAL: 122.3 °C
 Experiment no. 3
Boiling Point Determination
(Prelab Discussion)
Boiling Point

• Temperature at which the vapor pressure of the liquid is equal to the

pressure of the gas above it (or atmospheric pressure)

• Dependent on the applied pressure and the intermolecular force of

attraction between the liquid particles
Boiling Point Determination

Boiling points are determined for two reasons:

1. Used to characterize a new organic liquid
2. Knowledge of the boiling point helps to compare one organic liquid to
another as in the process of identifying an unknown substance
Objectives

• To assemble the proper set up for boiling point determination

• To perform and determine boiling point of different organic substances.

• To determine purity of organic substances by comparing the results obtained

between samples and between the actual and theoretical values.

• To explain the effect of structure of compound to its boiling point.

Procedure

1. Using a Bunsen burner, prepare 8 capillary tubes by sealing one end.

2. Place 5 drops of the sample into the bulblet/vaccine tube and place the
sealed capillary tube into the bulblet containing the sample with the
sealed end topmost.

3. Attach the bulblet to the thermometer with a ring of rubber tubing

around 3cm above the tip of the bulb or the capillary tube inside the
bulblet is at the same level as the thermometer bulb.

4. Immerse the setup on an oil bath.

Procedure

5. Increase the temperature of the bath gradually until a rapid and

continuous stream of bubbles comes out of the capillary tube and passes
through the liquid sample.

6. Remove the heat and allow the bath to cool by stirring continuously.

7. Take note of the temperature at the instant the bubbles cease to come
out of the capillary tube and just before the liquid enters it.
Procedure

Boiling point determination set-up

Procedure

Boiling point determination

Results
Experiment #2: Melting Point Determination
• Objectives:
 To assemble the proper setup for melting point determination;
 To perform and determine melting point of different organic
substances;
 Determine purity of organic substances by comparing the results
obtained between samples and between the actual and theoretical
values;
 To explain the effect of structure of compound to its melting point.
Introduction
• Melting Point
• It is the range of temperature at which the solid phase changes to liquid.
• It is the temperature at which the thermal motion of the molecules is just enough to
break down the lattice structure of the crystal.
• Crystal solids have sharp melting point because of the symmetry in
structure and in strength of bonds.
• Pure compounds have sharp melting point and this physical property can
be used to determine purity or presence of impurities.
• Mixed melting points method
• It provides a means of testing for the identity of two solids by examination of the
melting point behavior of a mechanical mixture of the two.
• It is valuable at certain points for the identification of unknowns.
Introduction
• Trends in meting point of organic compounds:
• For alkanes, the larger the molecule, the higher the melting point.
• For solids, the more ordered the molecule, the more energy is required to break the
intermolecular forces holding the molecules together.
• Odd number alkanes have a lower trend in melting points than even-numbered alkanes
because even-numbered pack well in the solid phase, forming a well-organized structure.
• Flat shape aromatic compounds have higher melting points compared to non-planar
hydrocarbons with similar molecular weights
• In the periodic table, melting point decreases from center going to the sides (left and
right); decrease from top to bottom.
• Ionic compounds have very high melting points.
• Presence of polar and hydrogen-bonding groups on organic compounds generally leads
to higher melting points.
Results and discussions
Samples Molecular weight Melting Point (Theoretical)
Naphthalene 128 80.26
Oxalic acid 90 102
Benzoic acid 122 122
Malic acid 134 130
Urea 60 133
Salicylic acid 138 158.6
Succinic acid 118 184
p-amino benzoic acid 137 187
Sodium benzoate 144 410
Naphthalene Benzoic acid Sodium benzoate Salicylic acid p-amino benzoic acid

Oxalic acid Succinic acid Malic acid Urea

Results and discussions
 Apparatus used to measure melting point:
 Thomas-Hoover Uni-melt melting point apparatus
 Thiele tube melting point apparatus
 Fisher-johns melting point apparatus
 Nalge-axelrod melting point apparatus
Stuart melting point apparatus SMP10
Experiment #3: Boiling Point Determination
Objectives:
 To assemble the proper setup for boiling point determination;
 To perform and determine boiling point of different organic
substances.
 Determine purity of organic substances by comparing the results
obtained between samples and between the actual and theoretical
values.
 To explain the effect of structure of compound to its boiling point.
introduction
• Boiling Point
 It is the temperature in which the vapor pressure is equal to the atmospheric pressure
 It can give information about their physical properties and structural characteristics of
compounds.
 It can also be used identify and characterize compounds.
 It is dependent on the kinetic energy of particles and varies with the surrounding
atmospheric pressure
Introduction
• Trends in Boiling point of organic compounds:
• Just like melting point, the relative strength of intermolecular forces
can affect boiling point of compounds.
• Presence of polar and hydroxyl groups can increase boiling point of
compounds.
• As the length of carbon chain increases, the boiling point also
increases.
• Increase in the length of carbon chain increases surface area of the
compound while branching of molecules decreases the surface area.
• Primary alcohols boil higher than secondary and tertiary alcohols.
Results and discussions

Sample Molecular weight Boiling point (Theoretical)

Acetic acid 60 118
N-hexane 86 68.6
N-pentane 72 36.1
N-butyl alcohol 74 117.7
Sec-butyl alcohol 144 112
Tert-butyl alcohol 74 82.2
Preliminary Topics
Content
• Electronegativity and Bond Polarity
• Polarity of Molecules
• Intermolecular Forces of Attraction
• Physical Properties of Organic Compounds
Electronegativity
• measure of an atom’s ability to attract electrons from a neighboring atom
to which it is bonded.

(Bruice, P., 2016)

Bond Polarity
• depends on the electronegativity difference of the two atoms in the
chemical bond

Electronegativity Type of Chemical

Difference Bond
>2 ionic bond
0.5 - 2 polar covalent bond
< 0.5 nonpolar covalent
bond

(Klein, D., 2017)

Sample Problem
What type of chemical bond is H-F bond?

Electronegativity Type of Chemical

Difference Bond
>2 ionic bond
0.5 - 2 polar covalent bond
< 0.5 nonpolar covalent
bond

(Klein, D., 2017)

Practice Exercise

Classify the following bonds as

ionic, polar covalent or non-polar
covalent.

1. Bond in HCl
Electronegativity Type of Chemical Bond
Difference
2. Bond in KF
>2 Ionic Compound 3. C-C bond in H3C-CH3
0.5 - 2 Polar Covalent Bond
4. C-H bond in H3C-CH3
< 0.5 Nonpolar Covalent Bond

(Klein, D., 2017)

Bond Polarity

(Bruice, P., 2016)

Sample Problem
Which bond is MORE polar? C–O or C–Cl
Given the electronegativity values of C (2.5), O (3.5), and Cl (3.0)
Practice Exercise
Which bond is MORE polar?
1. H–CH3 or Cl–CH3
2. H–OH or H–H
3. H–Cl or H–F
4. Cl–Cl or Cl–CH3
Bond Polarity
• Some helpful generalization in Organic Chemistry.

Chemical Bond Type of Chemical Bond

C–N, C–O, and C–F Polar Covalent Bond
H–N, H–O, and H–F
C–X Polar Covalent Bond
(X is F, Cl, Br, or I)
C–C, C–H, X–X Nonpolar Covalent Bond
Polarity of Molecules
Polar Molecules
• One end of the molecule is said to possess positive charges and whereas
the opposite end of the molecule has negative charges

• It must have
• polar covalent bond (one atom is more electronegative)

• the dipole moments must not cancel each other (symmetrical

molecules are less polar)
Polarity of Molecules
Polar Molecules

water ethanol acetone

dipole moment = 1.87 D dipole moment = 1.69 D dipole moment = 2.88 D
Polarity of Molecules
Nonpolar Molecules
• No positive or negative poles formed in the molecule.

• Generally symmetrical

• No dipole moment
Polarity of Molecules
Nonpolar Molecules

hexane benzene carbon tetrachloride

dipole moment = 0 D dipole moment = 0 D dipole moment = 0 D
Polarity of Molecules

(Klein, D., 2017)

Sample Problem
Identify whether each of the following compounds exhibits a molecular
dipole moment. For compounds that do, indicate the direction of the net
molecular dipole moment:

1. CHCl3
2. CH3OCH3
3. NH3
4. CCl2Br2
Sample Problem
Identify whether each of the following compounds exhibits a molecular
dipole moment. For compounds that do, indicate the direction of the net
molecular dipole moment:

5) 6) 7) 8)
Practice Exercise
• Identify whether each of the following compounds exhibits a molecular
dipole moment.
• For compounds that do, indicate the direction of the net molecular dipole
moment:

5) 6) 7) 8)
Intermolecular Forces

• These are attractive forces between molecules.

• Responsible for bulk properties of matter (examples: boiling point and

melting point)

• All intermolecular forces are electrostatic

Intermolecular Forces
Compare the melting point of the two solids.

I2 solid NaCl solid

mp = 114°C mp = 801°C
Dipole-dipole forces
• attractive forces between polar molecules
• electrostatic in nature
• the larger the dipole moment, the greater the force

(Klein, D., 2015)

Hydrogen bonding
• a special type of dipole-dipole interaction
• involves an electronegative atom (O, N and F) and a hydrogen in a polar
covalent bond

(Klein, D., 2015)

Dispersion forces (London dispersion forces)
• involve temporary dipoles induced in an atom or molecule by an ion or a
dipole

• exhibited by nonpolar molecules (compounds with no dipole moment)

• usually increases with molecular mass

• hydrophobic forces

• Dispersion forces exist among species of all types, whether polar or

nonpolar molecules.
Dispersion forces (London dispersion forces)

(Klein, D., 2015)

Sample Problem
Look at the structure of the following compounds:
Sample Problem
What type of intermolecular forces exists predominantly in the molecules of
the following compounds?

Compound Predominant Intermolecular Force of Attraction

pentanal
hexane
propionic acid
benzene
propan-1-amine
Sample Problem
Which of the following compounds would have hydrogen bonding with alike
molecules?
Application of Intermolecular Forces in Drug Binding
• Drugs bind to their target (example: enzymes, receptors, etc.) due to the
intermolecular force of attraction between the drug and the binding site.

Binding of Enalaprilate to the Active Site of Angiotensin-converting Enzyme (ACE)

(Patrick, G., 2013)
Physical Property
• Any property of a substance that can be observed without transforming
the substance into some other substance

melting point
Physical Property
• In studying organic compounds, the following are the common physical
properties that are being measured:

Physical
Properties

Melting Point Boiling Point Solubility

• Affected by intermolecular forces of attraction

Physical Property
• Compare the boiling point of the following compounds:

butane 1-chlorobutane 1-butanol

bp = -0.5°C [13] bp = 78.5°C [14] bp = 117.7°C [15]

• What is the predominant intermolecular forces present in the following

compounds?
Physical Property
• In general, the relative strength of intermolecular forces of attraction is:

Hydrogen bonding > Dipole-dipole Forces > Dispersion forces

butane 1-chlorobutane 1-butanol

bp = -0.5°C [13] bp = 78.5°C [14] bp = 117.7°C [15]
 Experiment no. 2
Melting Point Determination of Organic Compounds
(Post-lab Discussion)
Melting Point
• Temperature at which a given solid material changes from a solid state to a
liquid, or melts.

• Dependent on the intermolecular forces of attraction between the solid

particles and the packing of the crystal structure

solid liquid
Determination of Melting Point
Determination of Melting Point
How to operate a melting point apparatus?

https://www.youtube.com/watch?app=desktop&v=WjCWk9HJlqQ
Determination of Melting Point

sample before melting sample starts to melt sample melts completely

Determination of Melting Point
Heating Curve
Determination of Melting Point
Fast heating
• The result will be inaccurate since there is less time for the temperature of
the device and the sample to equilibrate.

• A higher temperature is observed because the device is heating faster but

the sample did not equilibrate yet with the device.
Determination of Melting Point
Slow heating
• The result will be accurate since there is sufficient time for the temperature
of the sample to equilibrate with the device.
Results
Accurate Melting Point Method

Sample Theoretical Melting Point (°C)

Benzoic acid 121-123
Sodium benzoate 436
Urea 132-135
Salicylic acid 158-161
Naphthalene 80-82
Factors that affect the Melting Point of Organic Compounds

• Chemical Bond Type

• Polarity
• Presence of Hydrogen bonding
• Molecular symmetry
• Molecular size
Factors that affect the Melting Point of Organic Compounds

Chemical Bond Type

• What is the chemical bond type between the two solids?
• Compare the melting points.

benzoic acid sodium benzoate

mp = 122.4°C mp = 436°C
Factors that affect the Melting Point of Organic Compounds

Chemical Bond Type

• Ionic solids has a higher melting point since ionic bonds (intramolecular
force) is stronger than intermolecular forces.

benzoic acid sodium benzoate

mp = 122.4°C mp = 436°C
Factors that affect the Melting Point of Organic Compounds

Polarity
• What is the predominant intermolecular forces present in the two solids?
• Compare the melting points.

benzoic acid naphthalene

mp = 122.4°C mp = 80.2°C
Factors that affect the Melting Point of Organic Compounds

Polarity
• Polar compounds have higher melting points since dipole-dipole forces are
stronger than dispersion forces.

benzoic acid naphthalene

mp = 122.4°C mp = 80.2°C
Factors that affect the Melting Point of Organic Compounds

Presence of Hydrogen bonding

• How many functional groups can form hydrogen bonds in the two solids?
• Compare the melting points.

benzoic acid salicylic acid

mp = 122.4°C mp = 158°C
Factors that affect the Melting Point of Organic Compounds

Presence of Hydrogen bonding

• Compounds with more functional groups that can form intermolecular
Hydrogen bonds have higher melting point.

benzoic acid salicylic acid

mp = 122.4°C mp = 158°C
Factors that affect the Melting Point of Organic Compounds

Molecular Symmetry
• Which molecule is more symmetrical?
• Compare the melting points.

resorcinol hydroquinone
mp = 109.8°C mp = 170°C
Factors that affect the Melting Point of Organic Compounds

Molecular Symmetry
• Symmetrical molecules are better packed in the crystalline structure.
Hence, they have higher melting points.

resorcinol hydroquinone
mp = 109.8°C mp = 170°C
Factors that affect the Melting Point of Organic Compounds

Molecular Size
• Compare the melting points.

butyric acid
mp = -5.7°C

palmitic acid
mp = 62.49°C
Factors that affect the Melting Point of Organic Compounds

Molecular Size
• Larger molecules have stronger dispersion forces, hence, the higher the
melting point.

butyric acid
mp = -5.7°C [10]

palmitic acid
mp = 62.49°C [11]
Exercise
Arrange the following based on INCREASING melting point.

I II III
Results

Effect of Impurities

Sample Melting Point (°C)

Benzoic acid
Impure benzoic acid
Effect of Impurity
• The impurity disrupts the intermolecular force of attraction that holds the
particles in the crystal structure

• Impure solids generally melt at the lower temperature and broader range
(> 2°C)