Experiment 6 6-1

GAS CHROMATOGRAPHY AND ANALYSIS OF UNKNOWNS

Introduction
This experiment deals with the separation and identification of organic compounds by the analytical
technique of gas chromatography (commonly called GC). Most natural products, such as petroleum, coal,
plant extracts and the biological components of our bodies, are complex mixtures of organic compounds. A
major task for the analytical chemist today is to design sensitive methods for separating such mixtures and for
identifying their individual components. In the technique of gas chromatography, the mixture is first
volatilized, in an oven, into a mixture of gases that become separated as they pass through a long column.
What makes the components of a mixture separate from each other? The answer has to do with intermolecular
forces. The idea is this -- molecules that have the weakest attractive forces are the easiest to separate from each
other and therefore move fastest through the system those with the strongest forces have the least tendency
to vaporize and separate, and are therefore the slowest to move in the column. In addition, of course, we
must remember that a small molecule tends to move faster than a big (heavier) one. There remains the
question: what are the different types of attractive forces among molecules, and how do these forces rank in
strength? In your lab work this week, you will:
A. Review basic ideas about intermolecular forces and about factors that affect the volatility of organic
compounds.
B. Learn about the analytical technique of gas chromatography.
C. Use GC analysis to identify the components of a mixture of compounds.
D. Use several identification tests to classify organic compounds based on functional groups and verify
the results of your GC analysis.
E. Construct molecular models of some compounds, and use the models to study different types of
intermolecular interactions.
A. INTERMOLECULAR FORCES
There are four major types of attractive forces that tend to hold molecules close together, and hence enable
substances to exist in the solid and liquid states. These intermolecular forces are listed below in the order of
their increasing strength.
1. dispersion forces
2. dipole-dipole forces
3. hydrogen bonding forces
4. electrostatic (or ionic) forces
Dispersion Forces:
All molecules are attracted to each other by very weak dispersion forces. How do these forces arise? The
idea is that an atom or molecule may be neutral as a whole (the number of protons equals number of
electrons), and yet at a given instant the distribution of the charges may not be completely symmetrical. This
instantaneous dispersion of charge in one molecule is said to induce an equal but opposite dispersion in a
neighboring molecule, making the two molecules capable of instantaneously attracting each other. Three
special points should be remembered about dispersion forces:
a) The molecules of all substances are attracted to each other by dispersion forces (particularly
hydrocarbon chains and rings).
b) Dispersion forces are extremely weak, but they are additive. So, bigger molecules have stronger
attractive forces.
c) Dispersion forces act only at very short distances. They are effective only when the molecules of a
substance are close together.
Experiment 6 6-2
Dipole-dipole Forces:
A dipole is a molecule, or part of a molecule, in which there is a permanent (not just instantaneous)
asymmetry in the distribution of charge. How do dipole-dipole forces arise? The idea is that if, within the
molecule, two atoms have significantly different electronegativities, the bond joining these atoms will act like
a dipole, that is it will have partial positive and negative charges at its ends. The sum of all bond dipoles gives
the net dipole strength of the molecule. Molecules with a net dipole attract each other, as illustrated here.
Special points to remember:
a) Dipole forces act between molecules in which two or more atoms have significantly different
electronegativities. Hydrocarbons have no dipole forces because C-H bonds are nonpolar. In contrast,
groups like C=O, C-O-H, C-O-C, and C-N, impart polarity and hence enhance dipole forces.
b) Dipole forces are stronger than dispersion forces.
c) In symmetric molecules, such as CCl4, although individual bonds are polar, the molecule as a whole
will be nonpolar since the dipoles will cancel each other out.
H-Bonding Forces:
Hydrogen bonding may be thought of as an extreme case of dipole-dipole attraction. Thus, O-H bonds are
strongly polar because the O atom is strongly electronegative. Furthermore, since the H atom is uniquely
small and positively polarized, it can attract towards itself another O atom from a different molecule. As the
O-H
...
O atoms pull together, the attractive forces become considerably stronger, hence the term "hydrogen
bonding". The diagram that follows illustrates H-bonding between molecules of an alcohol R-OH, showing
that O-H is the donor from one molecule, and an O (lone pair) is the acceptor on another molecule. The dotted
line between two molecules indicates H-bonding.
Note that other conformations of the molecules are also possible. Special points to remember:
a) H-bonding is much stronger than dipole-dipole interaction which in turn is much stronger than
dispersion forces. The most electronegative elements, in the order of their decreasing power, are: F
> O > N (but you will not encounter H-bonding of F in this course).
b) Visualize an H-bond as a linear 3-atom unit. H-bond strengths are: O-H
....
O > N-H
....
O > N-H
....
N.
c) O-H is a strong donor of H-bonds. H2O has two OH groups hence it has two good donor sites.
R-OH (in alcohols) has only one H-bond donor site. The N-H group (in amines) is a weak H-bond
donor.
d) The O atom (through its lone pairs of electrons) is a good H-bond acceptor. Examples are water,
alcohols, ethers, aldehydes and ketones, acids, esters. The lone pair on an N atom is a weaker H-
bond acceptor.
+
+
+ +
+
+
+
+
+
+

O
R
H
O
R
H
O
R
H
O
R
H
O
R
H
Experiment 6 6-3
e) Compounds that contain O-H groups (an alcohol, carboxylic acid, etc.) have strong intermolecular
forces, and will be less volatile (have a higher boiling point) than a corresponding compound without
O-H.
Electrostatic (Ionic) Forces:
Electrostatic interaction is very strong and takes place between ions (oppositely charged groups). You will
come across ions in salts and later in zwitterions (amino acids and proteins). Oppositely charged groups attract
and like charges repel. Special points:
a) Electrostatic forces are very strong, but they become weaker as the ions get further away from each
other.
b) Electrostatic interactions act in all directions. Remember that H-bonds tend to be linear, and that
covalent chemical bonds are directional.
Factors which Affect Physical Properties
The two most commonly studied physical properties of organic compounds are their melting and boiling
points, and their solubility (in water). Consider solubility first, and note that solubility means miscibility with a
solvent. So, if you ask yourself what makes two substances miscible, the answer should be that their
molecular structures are compatible with each other. It is therefore not surprising to find that solubility in
water:
a) is enhanced by polarity, H-bonding and small size
b) is opposed by nonpolarity (hydrophobicity) and large size.
What factors affect the melting/boiling point of a substance? The short answer is that melting requires
overcoming the intermolecular forces that hold molecules fixed in a solid and a little mobile in the liquid.
Boiling involves completely separating the molecules, which can then go into the gas phase. You would
therefore predict that compounds tend to be volatile (that is, have a low boiling point) if intermolecular
interactions are weak and compounds tend to be less volatile (that is, have a high boiling point) if
intermolecular interactions are strong. Let us consider four common factors: (1) molecular size (2) molecular
shape (3) polarity (4) H-bonding.
1. Molecular Size
First consider the alkanes, which are saturated hydrocarbons. Since these molecules are nonpolar
(hydrophobic), the only intermolecular forces will be dispersion forces. Now a small molecule has a small
surface area and shows little interaction. Longer chain hydrocarbons have larger surfaces and show stronger
interaction (the forces are additive). Try to interpret the accompanying data on boiling points (C) for open
chain alkanes.
Compound B.P.
methane C1 -163
ethane C2 - 89
propane C3 - 42
butane C4 0
pentane C5 36
hexane C6 69
heptane C7 98
octane C8 126
Experiment 6 6-4
2. Molecular Shape
Inspection of molecular models shows that branched molecules do not pack together as well as open chain
molecules. We would therefore expect branched isomers to have weaker interactions. On this basis, see if you
can interpret the accompanying data on boiling points (C) for branched and unbranched isomeric C6 alkanes.
Compound B.P.
hexane 69
3-methylpentane 63
2,3-dimethylbutane 58
2,2-dimethylbutane 50
3. Polarity
Because the C and H atoms differ very slightly in their electronegativities, C-H bonds are considered
nonpolar. Consequently, all hydrocarbon molecules are described as hydrophobic, their molecules being
attracted by dispersion forces only. In contrast, compounds containing O atoms (and to a lesser extent N)
are polar and are attracted by the stronger dipole-dipole forces. Here is an example. Propane is a gas (B.P. =
-42C) acetaldehyde, which has the same molecular weight and about the same size, is a liquid (B.P. =
+200C). Look at their structures and try to account for this big difference.
hydrocarbon aldehyde
dispersion forces dipole forces
(very weak) (stronger)
4. Hydrogen Bonding
We have already noted that H-bonding has stronger effects on physical properties than does dipole-dipole
interaction. H-bonding has a big effect on the volatility and solubility of substances. Consider first
compounds like alcohols whose molecules are good donors/acceptors in H-bonding:
(a) Volatility - Substances whose molecules can act as H-bond donors and acceptors will have strong
intermolecular attraction and so they tend to be not volatile (have a relatively high boiling point). But
is the attraction due to dipole forces or to H-bonding forces? Well, we know that O-H is a dipole
and thus contributes to dipole-dipole interaction. However, H-bonding is much stronger.
Consequently, molecules containing C-O-H prefer to align themselves not as weak dipoles (as in the
left structure below) but along the stronger H-bond (right structure):
OH as dipoles linear H-bond
relatively weak (wrong) much stronger (correct)
CH
3
CH
2
CH
2
CH
3
CH
2
CH
3
C O
CH
3
H
O C
H
CH
3
C O
CH
3
H
O
R
H
H O
R
O
R
H
O
R
H
Experiment 6 6-5
(b) Solubility - Water is an excellent H-bond donor and H-bond acceptor. Therefore, substances whose
molecules are H-bond donors and acceptors can H-bond extensively with H2O molecules, and so
tend to be soluble in (miscible with) the solvent water. However, this effect must be balanced against
the opposing hydrophobic forces of nonpolar segments of the molecule.
Finally we ask: what about substances such as ethers, esters, aldehydes and ketones, whose molecules have O
atoms with lone electron pairs, but do not have OH groups? These molecules are H-bond acceptors but not
donors. Again, consider the two factors discussed above:
(a) Volatility - Here, mutual intermolecular H-bonding is not possible hence attractive forces are weak,
and the compounds tend to be volatile.
(b) Solubility - Here, the molecules can still form H-bonds with H20 (which is an excellent donor) hence
the compounds tend to be miscible with water. But, of course, if a compound is largely
hydrophobic, it will be less soluble. (Did you understand these arguments?)
Summary of Intermolecular Forces
1. Hydrocarbons are hydrophobic molecules. Interaction is by dispersion forces only. Intermolecular
forces are very weak - but additive.
2. Ethers, esters, aldehydes and ketones have C-O or C=O bonds. Interaction is mainly by dipole-
dipole forces. Intermolecular forces are stronger than above.
3. Alcohols (R-OH) and carboxylic acids (R-COOH) have H-bonding. H-bonding supercedes dipole
forces intermolecular forces are strengthened by H-bonding.
4. Inorganic salts and salts of carboxylic acids are ionic. Ionic interaction involves very strong
electrostatic forces. Salts (cation-anion) are solids.
B. GAS CHROMATOGRAPHY
Gas chromatography (GC) is an analytical technique for separating and identifying chemical substances, based
on differences in their intermolecular forces and their volatilities. GC is one of the most widely used
techniques, not only in chemistry but also in the other sciences and in industrial labs throughout the world.
Why is gas chromatography so widely used? The main advantages of GC are that it is a simple and
inexpensive method of analysis, and that it provides a rapid and effective method of separating complex
mixtures of compounds. Analysis by GC can be highly sensitive (it can determine extremely small quantities
of a substance) and highly selective (it can identify specific substances in a complex mixture). In fact, GC is
applicable to any substance that can be volatilized, or one that can be converted into a volatile derivative, be it
in petroleum or in biological materials, industrial products or consumer goods.
Apparatus
The components of a gas chromatograph instrument are shown in the schematic diagram that follows. The
mobile phase, called the carrier gas, is an inert gas, usually helium. Compressed gas flows from a cylinder,
coming out through valves that control pressure and rate of flow, past an injector port (the entry point of the
sample), and through the coiled column that is the heart of the instrument. The column is packed with solid
particles coated with an oil of suitable polarity, depending on the mixture to be separated. In this experiment,
the column packing is coated with silicone oil of intermediate polarity. The gas then reaches a detector which
transduces the chemical signals received into electrical current in a pen recorder. The column and accessories
are all located in a thermostatically controlled oven, which maintains the required (high) temperature.
Experiment 6 6-6
GC Analysis
To carry out an analysis, a sample is injected from a syringe, through a rubber septum, into the heated injector
port where the liquid sample is vaporized. The carrier (helium) gas now drives the sample (which is a mixture
of component substances) through the column..
In this week's experiment, which involves a mixture of polar and nonpolar substances, the column has
moderately polar packing. As the mixture of gases passes through the column, the more polar substances will be
more strongly attracted to the packing material in the column, and the less polar substances will be less
attracted. Which substance comes off the column first? The answer to this question is as follows: the lowest-
boiling nonpolar (hydrocarbon) component of the mixture will be least retarded by the column it will be swept
through rapidly and come off the column first. Higher boiling and/or more polar compounds are retarded
more, and are therefore swept through more slowly, coming off later. Clearly, the most polar and highest
boiling compound in the mixture will come out last. The detector then signals the presence of each
component as it arrives from the column. The time it takes a certain compound to pass through the column
is called its retention time. This retention parameter can then be used to identify a particular substance in the
mixture. The retention time will be constant for a given substance as long as all of the parameters associated
with the separation are kept the same (column packing and length, oven temperature, carrier gas, gas flow
rate, etc).
GC Chromatogram
The output from the column is monitored as a scan or profile, in which the intensity of the detection signal
(vertical scale) is plotted as a function of time (or distance on a recorder chart, horizontal scale). This output
is called a scan or chromatogram. A typical GC scan for a mixture of two components, A and B, is
shown below. It is also usual to have a tiny quantity of air in the mixture. The chromatogram should show
the point of injection (at the moment the mixture was injected sometimes this is marked by touching the
column outlet port on the side of the GC which causes a deflection in the chromatogram), and the air signal
(always showing air coining out first), followed by the two signals for compounds A and B.
Experiment 6 6-7
Retention Time
In the above example, tA is the retention time of A, and tB that of B, both measured from a suitable starting
point. In theory, we would expect retention to be measured from the point of injection (where the arrow
points). However, it is technically simpler to take the air signal as the starting point, as in the diagram. In any
case, we note that component A came off first, and B later. This indicates that compound B had stronger
interaction with the column and was therefore retarded more than A. Since the column packing is moderately polar,
we may conclude that the molecules of A are less polar than molecules of B, so that compound A is probably
the more volatile (lower boiling) component of the mixture. Did you understand all that?
Identification of Unknown Compound
Having run a chromatogram for a known mixture (that is, a mixture of known substances, such as A and B in
the above example), GC provides a rapid and very effective method of finding out if a certain unknown
substance X happens to be A or B (or neither!). You simply inject a sample of X and look at the scan. If the
retention time of X coincides with that of A, the unknown is identified as compound A. As a confirmatory
check on this result, you mix a little of A with a little x, inject this mixture, and run the GC scan again.
(Question: What would you expect the result to be?)
When an experiment serves to identify the (unknown) components of a given mixture, the procedure is called
qualitative analysis. When the purpose is to determine the amounts or concentrations of substances, quantitative
analysis is applied. Gas chromatography gives both types of information. The following section explains how
a GC experiment is also a quantitative experiment.
Relative Concentrations of Components
Why are the two signals in the above chromatogram not equal in height, or width? The answer is that the
two components are probably present in unequal amounts. How can we find their relative amounts (or
relative concentrations)? We proceed as follows.
First, assume that the response of the detector for a given component is measured by the area under the
signal curve. To get the area, imagine the curve (one signal in the scan) to be an isosceles triangle, with peak
height H, and base width W, as the diagram here shows. Then the area under the curve is approximately
equal to the area of the triangle (expressed, say, in cm
2
).
Experiment 6 6-8
Next, assuming that the instrument detector is equally sensitive to both components, we can compare signal
areas for components A and B (is this always a valid assumption? How might you test this assumption?).
The ratio of the areas therefore equals the ratio of their concentrations in the mixture. Thus, GC provides a
method of quantitative analysis.
Resolution of Components
One of the vexing problems in chemical analysis is how best to achieve a good separation of the various
components in a mixture. Consider the above example. How good was the separation of A and B? In other
words, how efficient was the column? The answer requires a measure of the separation of the two peaks. In
chromatography, this measure is a parameter called the resolution factor, R. R is defined as the ratio of the
distance (separation) between the two peaks to the average width of the two bases. Thus,
separation of peaks = (tB - tA)
average base width = (1/2)(WB + WA)
resolution factor R = (tB - tA)/(l/2)(WB + WA)
All distances must be expressed in the same units, so that R becomes a dimensionless quantity. As a rule of
thumb, if R is bigger than 1, resolution of peaks is considered good if R is less than 1, we say the two
components have not been completely resolved. Finally, note that in real situations a mixture may have a
large number of components, and its chromatogram can be very complex, as the example here shows.
C. FUNCTIONAL GROUPS
As you learned earlier in this laboratory, groups based on O and N attached to carbon backbones can affect
the properties of organic compounds. These groups are called functional groups and they can be used to catalog
the millions of organic compounds. Functional groups are the reactive centers of molecules, and so it is the
functional groups that are most likely to undergo changes in chemical reactions.
The functional groups each exhibit a specific set of chemical properties which extends to the molecule of
interest. All of the compounds in that class will share many of the same chemical properties. There are over
twenty common functional groups in organic chemistry, the ten most common ones are found in the table on
the next page.
Many organic compounds contain two or more functional groups within the same molecule. For example,
the amino acids contain an amino group and a carboxyl group. As a result, one part of the molecule behaves
like a carboxylic acid while another portion of the molecule behaves as an amine.
Experiment 6 6-9
Experiment 6 6-10
In this laboratory, we are going to limit our study to the alkane, alkene, alcohol, aldehyde, and carboxylic acid
functional groups. Some of the molecules that we will use are multifunctional that is, they contain more than
one functional group.
The Alkanes:
These compounds are also referred to as the saturated hydrocarbons (all carbon-carbon bonds are single
bonds, and each carbon has four single bonds). The alkanes are relatively inert they do not undergo
reactions under conditions which compounds from other functional groups will react. In essence, these
compounds are molecules devoid of any other functional groups. In the reaction schemes that we are using
in this laboratory, any compound that fails to give a positive test for any other functional group should be
judged to be a member of the alkane functional group.
The Alkenes:
Compounds which contain a double bond between two carbons is classified as an alkene. Alkenes are also
known as unsaturated hydrocarbons. Remember that the double bond is made up of a sigma bond and a pi
bond. The pi bond is easily broken and accounts for the reactivity of this functional group.
The Alcohols:
Compounds which contain a hydroxyl group joined to a carbon atom (that is not a carbonyl carbon, C=O)
are members of the alcohol class. These compounds can be subclassified as primary alcohols (the O is
bound to a C which is bound to a single alkyl group), secondary alcohols (the O is bound to a C which is
bound to 2 other alkyl groups), or tertiary alcohols (the O is bound to a C which is bound to three other alkyl
groups). The general formula for an alcohol is often abbreviated as R-O-H.
The Aldehydes & Ketones:
Both the aldehyde and ketone classes of compounds contain a carbonyl group (C=O). Aldehydes have at
least one hydrogen attached to the carbonyl carbon ketones have two alkyl groups attached to the carbonyl
carbon. Therefore, the carbonyl carbon will always be located at the end of a carbon chain in aldehydes. The
aldehyde functional group is abbreviated CHO (not COH, why?) and the ketone functional group is
abbreviated as RCOR. The chemical properties of aldehydes are different from the ketones for example,
aldehydes are easily oxidized to carboxylic acids whereas ketones cannot be further oxidized.
The Carboxylic Acids:
Carboxylic acids contain the carboxyl functional group (RCOOH). These compounds are all weak acids
(what is the difference between a strong acid and a weak acid?).
D. FUNCTIONAL GROUP TESTS
Each functional group has a particular set of chemical properties that allow it to be identified. Some of these
properties can be demonstrated by observing solubility, or chemical reactions which result in color changes,
precipitate formation or other visible changes.
Solubility Tests
Most organic compounds are not soluble in water, except for low molecular weight compounds which are
generally limited to compounds containing oxygen or nitrogen on carbon skeletons of five or fewer carbons.
Carboxylic acids form solutions that yield an acidic response (pH < 7) when tested with litmus or pH paper.
Ketones, aldehydes and alcohols that are soluble in water will form neutral solutions (pH = 7). Amines
(nitrogen containing compounds) will produce basic solutions (pH > 7).
Experiment 6 6-11
Compounds that are insoluble in pure water should be tested for solubility in 6 M NaOH. Carboxylic acids
that are insoluble in water will form a soluble sodium salt that will dissolve in 6 M NaOH through a
neutralization reaction. Likewise, basic compounds will dissolve in 6 M HCl. Compounds that are insoluble
in any of these solutions will include alkanes, alkenes, and high molecular weight alcohols, aldehydes and
ketones.
Bromination Test for Alkenes
Alkenes can readily add bromine to the double bond, forming dihalides. An alkene added to a solution of
bromine in cyclohexane will quickly remove the red color of bromine as the addition reaction takes place.
The removal of the red bromine color is a positive test for an alkene.
Ceric Nitrate Test for Alcohols
The ceric nitrate test is a qualitative test for the hydroxyl functional group of alcohols. If an alcohol is added
to the yellow ceric nitrate solution, a red ceric complex is formed. Therefore a change in color from yellow to
red is a positive test for alcohols.
Tollens Test for Aldehydes
Aldehydes can be distinguished from ketones by the Tollens test, because aldehydes are easily oxidized to
carboxylic acids, while ketones are not. The Tollens reagent is a solution of silver nitrate in aqueous
ammonia. The silver ion is the oxidizing agent which is reduced to silver metal as the aldehyde is oxidized to
the carboxylic acid. The positive Tollens test is the appearance of a silver mirror on the wall of the test tube,
or a gray to black precipitate of silver metal. The carboxylic acid that is formed in this reaction is quickly
neutralized to the soluble salt of the acid by the ammonia that is present in the reaction.
The tests described above are just a few of the many possible assays that are used to determine the
functionality of organic compounds.
[Ce(NO
3
)
6
]
2
+ROH [CeOR(NO
3
)
5
]
2
+HNO
3
(yellow)
(red)
RCOOH+NaOH RCOO

Na
+
(aq)+H
2
O
RNH
2
+HCl RNH
3
+
Cl

(aq)
insoluble solublesalt
C C
+Br
2
C
Br
C
Br
alkene
(colorless)
bromine
(red)
alkylbromide
(colorless)
RCHO+2[Ag(NH
3
)
2
]
+
+2OH

RCOO

NH
4
+
+ 2Ag(s)+H
2
O+3NH
3
aldehydeTollensreagent solublesalt
silver
mirror
Experiment 6 6-12
E. PROCEDURE
This lab will be done with a partner.
In this experiment, you will run the following compounds through GC analysis and through each of the
functional group tests. You will also be given an unknown mixture (make sure to record your unknown
number) that will contain two of the following compounds. Using GC analysis and functional group analysis,
you will make a determination of the compounds in your mixture.
Compound MW
BP (C)
Hexane 86.14 69
1-Hexene 84.16 64
1-Hexanol 102.18 157
Hexanal 100.16 131
Hexanoic acid 116.16 205
trans-2-hexen-1-ol 100.16 156
2,3-dimethylbutane 86.18 50
3,3-dimethyl-2-butanol 102.18 120
While you are waiting to use the GC, you may begin the functional group analysis on each of the known
compounds and your unknown.
Gas Chromatography
1. Your instructor will show you the gas chromatography apparatus and will demonstrate its operation.
Compare the apparatus with the schematic diagram in your experiment. Make sure you understand how
the instrument works.
2. Your instructor will show you how to inject 3 microliters of the known mixture and get its GC scan. Of
course, because gases travel rapidly, each experiment will be very short! Make sure to thoroughly rinse
the syringe with methylene chloride before and after each injection.
3. After taking the scan of the knowns and of your unknown, you will be told to return to your lab bench
where you will complete the calculations
4. Examine the scan of the known mixture. You will need a sharp pencil and a ruler.
a) Draw vertical lines to locate the air peak, and the peak tops for each of the compounds.
b) Measure each retention time from the position of the air peak. Read distances in centimeters, to the
nearest 0.1 cm. Enter the distances in a table in your notebook, for reference.
5. Next, examine the scan of your unknown mixture.
a) Measure the retention times as you did for the knowns.
b) Compare retention times for the unknowns with the data for the known. Do not expect perfect
agreement!
c) Identify the two compounds in your unknown.
d) In your report, enter the data and results for the unknown mixture.
6. Now get the areas under the two curves in the GC scan of your unknown.
a) For each of the two curves, carefully draw straight lines to simulate an isosceles triangle. Measure the
heights and the base widths (show these on the chromatogram).
b) Calculate the areas under the two curves. You may need help. Enter the results in your report.
7. Finally, calculate the resolution factor R for your unknown. Enter the result in your report.
Experiment 6 6-13
Functional Group Analysis
SAFETY NOTES:
1. Strong acids are used in several procedures. Eye protection must be worn at all times.
Gloves (blue nitrile) should also be worn while carrying out these analyses. If you should get
any liquids on your hands, wash the area immediately with running cold water and contact
the instructor.
2. Make sure to dispose of excess reagents as instructed:
a. Organic compounds need to go into the organic waste container in the waste hood.
b. Tests involving heavy metals (cerium) go into containers labeled for heavy metal waste.
c. Materials involving the Tollens reagent must be neutralized immediately after use by
pouring them into the beaker of 6 M nitric acid located in the waste hood.
3. Disposable glassware should be placed in the broken glass containers.
The following tests will be carried out on the known compounds as well as your unknown mixture. You
should prepare a table with 7 columns one for the compound names and 6 for the tests. You will need to
leave space for 9 rows since there are 8 known compounds and your unknown to test.
Solubility in water:
Place 1 mL water into nine 10x75mm test tubes. Add 3 drops or several crystals of the compound to be
tested (one compound per tube) to the water. Place a stopper in the tube and thoroughly mix the contents.
Allow each tube to rest for 1 minute. Record your observations in your table. If two layers form or if the
sample remains cloudy then the compound is not soluble in water if the transparent solution does not
contain visible boundaries then the compound is soluble in water. Retain samples for the pH test below.
pH test:
Compounds that are soluble should be tested with litmus or pH paper obtain a drop of the aqueous
solution on the end of a clean stirring rod and touch it to the test paper. Record whether the pH is acidic
(blue litmus turns red pH < 7), neutral (neither litmus paper turns color pH = 7) or basic (red litmus paper
turns blue pH > 7). Soluble solutions do not need to be tested with 6 M NaOH. Dispose of samples in the
organic waste container.
Solubility in 6 M NaOH:
For water insoluble compounds, add 3 drops or several crystals of each compound to 1 mL of 6 M NaOH.
Record your observations. Samples should be disposed of in the organic waste container.
Note: Since none of our compounds are basic (amines) we will not perform a solubility test in 6 M HCl.
Bromination Test for Alkenes:
Place 10 drops of the test compound into a 10x75 mm tube. Add 2 drops of bromine solution (Br2 in
cyclohexane) one drop at a time. Record your observations in the table in your notebook. Place the wastes in
the container labeled halogenated hyrdocarbons.
Ceric Nitrate Test for Alcohols:
For water soluble compounds: In a 10x75 mm test tube, mix 1 mL ceric nitrate solution with 6 drops of the
test compound. Carefully mix the sample. Record your observations in your notebook. Place the wastes in
the container labeled heavy metal wastes.
For water insoluble compounds: In a 10x75 mm test tube, dissolve 3 drops of the test compound in 2 mL of
dioxane. Add 1 mL ceric nitrate solution to the test sample. Carefully mix the sample. Place the wastes in
the container labeled heavy metal wastes.
Experiment 6 6-14
Tollens Test for Aldehydes:
You should have a 100 mL beaker with lukewarm water prepared in case you need to gently heat this
reaction. Use a heating mantle and controller (on a low setting) to warm the beaker containing water.
For each sample to be tested, prepare the following (NOTE: all glassware must be extremely clean):
To a 13x100 mm test tube, place 5 drops of aqueous 5% silver nitrate solution and 1 mL deionized
water. Add 1 drop 5% NaOH. Add fresh 1 M aqueous ammonia dropwise with mixing until the precipitate
just dissolves (excess ammonia will inhibit the reaction). Add 4 drops of the test compound. Allow the
reaction to proceed for 2-3 minutes. If no reaction is observed, then gently heat the reaction in the water
bath (excess heating will cause the Tollens reagent to decompose and give a false positive test) for 2-3
minutes. If the test tube is clean, a silver mirror will appear otherwise, a gray to black precipitate may be
formed as a positive test. Record your observations in your notebook. Dispose of these samples by pouring
them into a beaker of 6 M nitric acid found in the waste hood.
F. MOLECULAR MODELS
1. Construct two, duplicate, models of propane (C3 alkane).
a) Try to stack the two molecules, matching the three C atoms. You are now simulating intermolecular
attraction, the only forces available being nonpolar (dispersion) forces of hydrocarbon.
b) Connect the above two propane molecules into a single chain, making one molecule of hexane (C6
alkane) in its extended zigzag conformation. Your partner will also have constructed a hexane
molecule.
c) You and your partner can now see how two extended hexane molecules can stack together so as to
maximize their interaction by nonpolar (dispersion) forces. Remember that, although dispersion
forces are extremely weak, nevertheless they are additive.
d) Turn to your report and answer question 1. Do not dismantle your model.
2. Convert your model of hexane into 2,2-dimethylbutane.
a) Detach the two end CH3 groups of hexane, and remove the two H atoms of carbon-2 in the resulting
butane chain. Now attach both methyl groups at the carbon-2 position, and put the two H atoms at
the ends of the chain. You have made 2,2-dimethylbutane, the doubly branched isomer of hexane.
b) You and your partner can now see how two branched molecules find it more difficult to pack
together than two extended molecules. The idea here is that branching weakens intermolecular forces.
c) Turn to your report and answer question 2. Do not dismantle your model.
3. Rearrange your model of 2,2-dimethylbutane into hexanal.
a) First return the branched molecule, 2,2-dimethylbutane, to its original open chain form, hexane.
Then remove two H atoms on carbon-1 and replace them with an O atom attached by a double
bond (two curved links) making the aldehyde hexanal.
b) You have done the following: removed 2H atoms (dehydrogenation), and added one O atom
(oxygenation). This explains why we say that aldehydes and ketones are two stages of oxidation above
the corresponding hydrocarbon.
c) Since the O atom is strongly electronegative, the C=O (carbonyl) group is polar. Observe the dipole
(C slightly positive, O slightly negative). The presence of a dipole in hexanal makes dispersion forces
unimportant intermolecular attraction is now dominated by the stronger dipole-dipole forces.
d) You and your partner can now demonstrate dipole-dipole interaction between two aldehyde
molecules. Refer to the section on dipole forces.
e) Turn to your Report and answer Question 3. Do not dismantle your model.
4. Convert your model of hexanal into the alcohol 1-hexanol.
HO-CH2-CH2-CH2-CH2-CH2-CH3
a) Disconnect the O atom and its double bond from the aldehyde molecule. Add 2 H (hydrogenation
= chemical reduction). One H atom goes on carbon-1, the other makes the OH group which you then
attach to the same carbon-1. You have made the (primary) alcohol 1-hexanol.
Experiment 6 6-15
b) Since the OH group is a very good H-bond donor/acceptor, you would expect intermolecular attraction
between alcohol molecules to be not the above dipole forces but the much stronger forces of H-
bonding.
c) You and your partner can now demonstrate how two alcohol molecules can arrange themselves in
two different ways:
1- with the two OH groups aligned antiparallel as dipole-dipole
2- with the two OH groups aligned O-H
...
O in a linear H-bond. Refer to the section on H-bonding.
Since H-bond forces are much stronger than dipole forces, which way do you think alcohol
molecules would tend to align themselves? Finally, turn to your report and answer questions 4
and 5.
G. DISCUSSION QUESTIONS FOR YOUR LABORATORY WRITE-UP
Points to cover in your report remember this is not an exhaustive list, but the points that must be covered:
1) Table of retention times for the known organic compounds and your unknown.
2) Copies of each of the chromatograms for each sample.
3) Prediction of the composition of your unknown mixture based on GC retention times and relative
amounts of the compounds based on the GC peaks for those compounds. You should be able to
report these to at least 3 significant figures. Report as percent composition (area of peak 1/total
area of the 2 peaks)*100% -- remember the percentages of both peaks need to add up to 100%.
Remember to show your calculations.
4) Calculate the resolution factor for the mixture analysis. Was the resolution complete? Explain.
5) Table of results from the functional group tests for known samples and your unknown.
6) Prediction of the composition of your unknown mixture based on the functional group analysis.
7) Verification of your conclusion based on the GC and functional group analysis results.
Q-1 Arrange the four types of intermolecular forces in order of increasing strength.
Q-2 Predict the left-to-right order of rising boiling point (that is, decreasing volatility) for the following:
(a) heptane (b) 2-heptanone (c) 2,2-dimethylpentane (d) 2-heptanol.
Q-3 If you were to analyze, by gas chromatography, a petroleum product which is a mixture of
hydrocarbons, which one of the following GC columns would you use? a) ionic column,
b) mainly nonpolar column, c) strongly polar column, d) empty column, e) column filled with
petroleum. Explain your reasoning.
Q-4. You have seen how two molecules of propane (C3 alkane) attract each other by the very weak
dispersion forces. You applied this concept to the case of a longer chain hydrocarbon (hexane, C6
alkane).
(a) How many carbons in one hexane molecule get close to centers in the other molecule? Explain
your answer.
(b) Why are intermolecular attractive forces (dispersion forces) stronger in hexane, relative to
propane?
(c) Which of these two hydrocarbons, propane or hexane, is less volatile (that is, boils at a higher
temperature)?
Q-5. You converted your model of hexane into its branched isomer 2, 2-dimethylbutane.
(a) As two molecules of 2,2-dimethylbutane move about, how many C atoms of one molecule will
normally get close to C atoms of the other?
(b) Compare hexane and 2,2-dimethylbutane. In which compound are intermolecular forces
weaker?
(c) What would you conclude is the effect of branching on volatility of hydrocarbons? (Hint: See
text.)
Experiment 6 6-16
Q-6. You converted your model of hexane into hexanal.
O=CH-CH2-CH2-CH2-CH2-CH3
This molecule, a aldehyde, contains a carbonyl group. Therefore, intermolecular attraction here is
dominated by dipole forces (dispersion being much weaker). Draw a model that shows dipole-dipole
interaction between two molecules of hexanal. Draw 2-dimensional zigzag skeleton structures.
Q-7. Next, you simulated a hydrogenation reaction (chemical reduction) by converting your model of
hexanal into the corresponding primary alcohol 1-hexanol.
HO-CH2CH2CH2CH2CH2CH3
Alcohol molecules have O-H groups and the O-H group is a strong H-bond donor/acceptor.
Intermolecular attraction of alcohols is therefore dominated by the much stronger forces of H-
bonding. Draw a structural representation of two molecules of 1-hexanol, showing intermolecular
(linear) H-bonding interaction. Draw 2-dimensional zigzag skeleton structures.
Experiment 6 6-1
Cl22 Prelab Assignment Name
Section
GAS CHROMATOGRAPHY AND FUNCTIONAL GROUP ANALYSIS
1. List three advantages of the analytical technique of gas chromatography.
1-
2-
3-
2.. Why does a GC apparatus have an oven?
3. What are the four types of intermolecular forces that are referred to in the text?
1-
2-
3-
4-
4. Dimethyl ether (CH
3
-O-CH
3
) is a gas, but its isomer ethanol (CH
3
-CH
2
-OH) is a high boiling liquid.
Explain this in terms of intermolecular forces.
5. Name the functional group or groups that appear in each of the following compounds. Also give the
IUPAC name for each compound
IUPAC Name Functional Group
a. CH3CH2OH
b. CH3CH2COOH
c. O=CHCH2CH2CH3
d. CH3CH=CHCH2CH3
e. CH3CH(OH)CH2COCH2CH3
Experiment 6 6-2
6. Using the following compounds, predict the results of the following functional group tests. Mark (+) to
indicate a positive test.
Compound Water
Solubility
pH Solubility
in 6 M
NaOH
Brominati
on Test
Tollens
Test
Ceric
Nitrate
Test
CH3CH2OH
CH3CH2COOH
O=CHCH2CH2CH3
CH3CH=CHCH2CH3
CH3CH(OH)CH2COCH2CH3
7. Draw the structures of the 8 known compounds that will be used in this laboratory and identify the
functional groups:
Hexane
1-Hexene
1-Hexanol
Hexanal
Hexanoic acid
trans-2-hexen-1-ol
2,3-dimethylbutane
3,3-dimethyl-2-butanol