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Carboxylic acids
Ketones (>C=O) -one -oic acid
(-COOH)
Acid amides
Amines (-NH2 ) -amine -amide
(-CONH2 )
Acid chlorides
-oyl chloride Esters (-COOR) -oate
(-COCL)
Functional Functional
Prefix Prefix
group group
Sturctural Isomerism
Componds having the same molecular formula but different
structures:
• Compounds having the same molecular formula but different
arrangement of carbon chains are called chain or nuclear isomers.
For example (i) pentane, isopentane and neopentane (ii) hexane, 2-
methulpentane, 3-methylpentane, 2,3-dimethylbutane and 2,2-
dimethulbutane etc
• Compounds having the same structure of the carbon chain but
differing in position of multiple bonds, functional groups or
substituents are called position isomers. For example, (i) but-1-ene
and but-2-ene (ii) prpan-1-ol and propan-2-ol (iii) o-,m- and p- xylenes
etc.
• Compounds having the same molecular formula but different
functional groups are calledfunctional isomers. For example, (i)
alcohols and ethers (ii) aldehydes and ketones (iii) alkynes and
dienes (iv) various amines (1o , 2o , 3o ) (v) cyanides and isocyanides
etc.
• Compounds having the same molecular formula but different number
of carbon atoms on either side of the functional group (O,S or NH)
are caled metamers. For example, (i) diethyl ether and methyl n-
propyl ether (or isopropyl methyl ether). 2-pentanone and 3-
pentanone are position isomers as well as metamers.
• Isomers obtained by 1,3-migration of a proton from one polyvalent
atom to the other within the same molecule are called tautomers. If
one tautomer contains a keto group and the other the enol group,
such a tautomerism is called keto-enol tautomerism. For example,
acetaldehyde and vinyl alcohol.
• The percentage of enol form is negligible in simple aldehydes and
ketones, ie, acetone, acetaldehyde etc. The percentage of enol form,
however, increases, if the enol form is stabilized by intramolecular H-
bonding. For example, the percentage of enol form in acetoacetic
ester is 7% while that in acetylacetone is 76%.
Stereoisomerism
Isomers which have the same structures but differ in the relative
arrangements of atoms or groups in space are called stereoisomers. It is of
three types, i.e. conformational isomerism, optical isomerism and
geometrical isomerism.
Geometrical Isomers: Stereoisomers which have the same structural
formula but differ in the spatial arrangement of atoms around the double
bond are called geometrical isomers. The isomer in which the two similar
atoms/groups lie on the same side of the double bond is called the cis-
isomer while that isomer in which the two similar atoms/groups lie on the
opposite side of the double bond is called the trans-isomer.
• The necessary and sufficient condition for a molecule to exhibit
geometrical isomerism is that each ot the two carbon atoms of the
double bond must have different atoms/groups which may be same of
different. Gor example , alkenes of the types abC=Cab and abC=Cde
show geometrical isomerism
• Compounds containing C=N and N=N also show geometrical
isomerism
• 1,2-1,3 and 1,4-disubstituted cycloalkanes also show geometrical
isomerism
• The dipole moment of a cis-isomer is higher than that of a trans-
isomer
• E and Z configuration of geometrical isomers
○ Give priority to the four groups attached to the double bonded
C-atoms. Higher the atomic number of the atom of the group
attached to the double bonded carbon atom higher will be its
priority. If priority cannot be decided the atoms directly attached
to double bonded C-atoms then next atoms of the group are
compared
○ If two higher priority groups are on the same side of the double
bond then it is called a Z-isomer otherwise it is called an E-
isomer
Conformational Isomerism: The infinite number of momentary
arrangement of the atoms in space which result through rotation about a
single bond are called conformations or rotational isomers
• Ethane has infinite number of conformations, of which, only two, i.e.
staggered and eclipsed are important. The staggered conformation of
ethane is more stable than the eclipsed conformation by about 3.0
kcal or 12.55 kJ mol-1
• Important conformations of n-butane are staggered (or anti), gauche
(or skew), partially eclipsed and fully eclipsed. Their relative stability
is in the order:staggered>gauche>partially eclipsed>fully eclipsed
• Cyclohexane exists in two non-planer conformations, i.e., chair and
the boat form. Both these conformations are free from angle strain
(i.e., have tetrahedral angles)
• The boat form of cyclohexane is less stable than the chair form by
about 44 kJ mol-1
• The two conformations of cyclohexane cannot be separated but ar
readily interconvertible
In this reaction, the oxygen atom of one water molecule collides with a hydrogen
atom of the second water molecule. A lone pair of the oxygen atom becomes the
new O-H bond in the hydronium ion. Because a hydrogen can only be fully bond
to one other atom at a time, the old O-H bond is lost. The electron pair of the old
O-H bond becomes a lone pair, sole property of the oxygen atom of hydroxide ion.
This very simplistic step-by-step bookkeeping description of all the bonding and
electron changes in a reaction is called the reaction mechanism. Study,
understanding and prediction of reaction mechanisms is at the very heart of
reactions in organic chemistry. Mastering the fundamentals of reaction
mechanisms is a fundamental survival skill for students of organic chemistry. You
will use them every day that you study organic chemistry.
Above we used several lines of text to describe the bonding changes in a single
step of a reaction mechanism. A reaction mechanism might have ten steps or more,
making such descriptions very cumbersome. A shorthand notation that summarizes
these changes has thus been developed. This notation, called curved arrow
formalism, provides a rapid way of drawing bond and electron changes in a given
mechanism step. They are also useful to indicate electron changes between a set of
contributing resonance structures.
Each curved arrow with two barbs on the head represents the shift of one
electron pair. (Later we will encounter single-barbed curved arrows that represent
the shift of single electrons.) The curved arrows shows the direction of electron
flow. The tail shows the electron origin, and always come from an electron source,
usually a lone pair or bonding pair from a σ or π bond. The head of the arrow
indicates the electron pair destination, either as a new lone pair or a new bond. If
the arrowhead points to another atom, that atom must either have an open octet and
thus be able to accept the electron pair, or have an electron pair that can be
displaced by the incoming electron pair. Electrons never flow from atoms which
are electron-poor to atoms which are electron-rich, so a curved arrow will never
point from an atom with a positive charge to an atom with a negative charge.
The tail of the curved arrow on the right starts at the oxygen lone pair, meaning this
curved arrow shows a bonding change for this lone pair. The head of the curved
arrow points to the space between the oxygen and hydrogen atoms, meaning the
electron pair ends in that space as a bond between the oxygen and the hydrogen.
The hydrogen that accepts a new bond to oxygen must give up a pair of electrons
because it cannot have more than two valence electrons at a time. Thus, the old O-
H bond is displaced by the new electron pair from the other oxygen atom. The
curved arrow on the left indicates the electron pair that was the O-H bond becomes
a lone pair on the oxygen of the hydroxide ion.
If the arrow starts at a bond between two atoms, then that bond is broken. If
the arrow ends between two atoms, then a new bond is formed between those
atoms. (If the atoms are already bonded, then a double or triple bond results.)
The process of drawing a curved arrow mechanism is also commonly called
"electron pushing."
When drawing curved arrows, the start and stopping points of the arrows are
critical. Things that make no difference are where the arrows curve up or down, or
whether they start or stop at the top or bottom of an atom. The arrows you draw
may therefore look different than the arrows shown in this tutorial.
Note also the changes in formal charge that result from the electron changes. If an
atom shares a lone pair that it used to have all to itself then its charge decreases by
one (i.e., neutral atom become +1). If an atom gains a bonding electron pair all to
itself as a lone pair then its charge increases by one unit (i.e., a neutral atom
becomes -1). The charge is conserved in this mechanism step. The total charge on
the left (zero) is the same as the total charge on the right (-1 +1 = 0). Charge is
conserved in all mechanism steps. You should make a habit of checking your work
against this point to minimize errors.
Lone pairs are often involved in reaction mechanisms, so you should be in the
habit of drawing all lone pairs. It is also important that your curved arrows be
drawn neatly and precisely, clearly showing the atomic origin of the electron pair
at the tail of the curved arrow and the electron pair destination at the head of the
arrow.
Example 1: Provide the curved arrows for the reaction of hydroxide and
hydronium ions to form two molecules of water.
Example 2: Draw the product(s) of the following mechanism step based upon the
curved arrows.
Exercises:
Provide curved arrows that show how the following mechanism steps might occur.
Provide the product(s) for the following mechanism steps based upon the curved
arrows.
Lewis acid: A molecule or ion that accepts a pair of electrons to form a new
covalent bond (same as electrophile).
Lewis base: A molecule or ion that shares a pair of electrons to form a new
covalent bond (same as nucleophile).
The oxygen of hydroxide ion bears a formal charge of -1. The hydrogen of
hydrogen chloride bears a δ+ charge because chlorine is more electronegative than
hydrogen and thus the H-Cl bonding electron pair is unequally shared. We can
envision the start of the acid-base reaction between hydroxide ion and hydrogen
chloride as an electrostatic attraction between the opposite charges. As the reaction
proceeds, the oxygen atom of hydroxide ion shares a lone electron pair with the
hydrogen atom of hydrogen chloride, as shown with the curved arrow in the
reaction above. This simple reaction shares one feature in common with the
majority of reactions that you will encounter in your study of elementary organic
chemistry. One species in the reaction shares an electron pair (a Lewis base) with
another species (a Lewis acid) to make a new covalent bond. Application of this
electron sharing idea to any reaction gives you an excellent chance at starting to
figure out the mechanism for most common organic reactions.
Because of the ubiquity of electron pair sharers and acceptors in organic reactions,
we assign special and distinct terms to these species. A molecule or ion that
accepts a pair of electrons to make a new covalent bond is called
an electrophile (from the Greek for "electron loving"). An electrophile is the same
thing as aLewis acid. Any molecule, ion or atom that is electron deficient in some
way can behave as an electrophile. Electron deficiency would include a formal
positive charge (methyl carbocation), a partial positive charge (δ+), usually in
conjunction with a polar bond (such as H-Cl) or an open octet (borane). "E" or
"E+" are common abbreviations for generic electrophiles.
Typical electrophiles:
A molecule or ion that donates a pair of electrons to form a new covalent bond is
called a nucleophile (from the Greek for "nucleus loving"). A nucleophile is the
same thing as a Lewis base. Any molecule, ion or atom that has electrons that can
be shared can be a nucleophile. The most common indications that electrons are
available to be shared are formal negative charge (iodide ion), a partial negative
charge (δ-), usually in conjunction with a polar bond (methyl magnesium
bromide), aπ bond (isobutylene) or lone pairs (ammonia). "Nuc" or "Nu" are
common abbreviations for generic nucleophiles.
Typical nucleophiles:
The study of reaction mechanisms is central to the study of organic chemistry at
any level. Therefore identification of electrophiles and nucleophiles is a critical
organic chemistry survival skill. Examination of a structure for the features
discussed above is one way to identify how a molecule or ion might behave in a
reaction. Another way is by considering the curved arrows. Because electrons
flow from an electron source to a place of electron deficiency, a curved arrow
points away from a nucleophile and to an electrophile. This does not work in every
reaction, however. In some reactions, the electron flow could go in either
direction, and there are no distinct nucleophiles and electrophiles. Such reactions
are uncommon in a course of this level.
Solution 2: Examine each structure for the charge distribution and electronic
features discussed above.
a. Bromide ion: This atom has four lone pairs and a formal negative charge,
suggesting it is electron-rich and can therefore function as a nucleophile. It has
none of the features that would suggest it might behave as an electrophile.
b. Ammonium ion: This ion has a formal positive charge, suggesting it is electron-
poor and can therefore function as an electrophile. It has no lone pairs or areas of
negative charge, suggesting it will not function as a nucleophile.
c. Water: The oxygen atom of water has two lone pairs and a δ- charge (oxygen is
more electronegative than hydrogen). This suggests that water can behave an a
nucleophile. Each hydrogen atom bears a δ+ charge, so the molecule can behave
as an electrophile as well. Many molecules can be both nucleophiles and
electrophiles. How they behave depends upon what they react with. For example,
if water is reacted with an electrophile, the water will behave as a nucleophile.
Exercises:
Identify the nucleophiles and electrophiles in each mechanism step shown below.
We will use three molecules (CO2, CO32- and NH4+) as our examples on this guided
tour of a simple method for drawing Lewis dot structures. While this algorithm
may not work in all cases, it should be adequate the vast majority of the time.
2. If there is more than one atom type in the molecule, put the most metallic or
least electronegative atom in the center. Recall that electronegativity decreases as
atom moves further away from fluorine on the periodic chart.
4. Count the electrons around each atom: are the octets complete? If so, your Lewis
dot structure is complete.
5. If the octets are incomplete, and more electrons remain to be shared, move one
electron per bond per atom to make another bond. Note that in some structures
there will be open octets (example: the B of BF3), or atoms which have ten
electrons (example: the S of SF5).
Resonance: Vocabulary
Exercise Solutions
These structures are similar in that the have the same types of bonds and electron
positions, but they are not identical. The position of the carbon-oxygen double
bond makes them different. In structure A the double bond is with the top oxygen
atom, in B with the right hand oxygen atom, and C with the left hand oxygen
atom. These oxygen atoms are at different places in space, so these are different
structures. Consider this analogy: when the hands on a clock are at a 90o angle, the
time could be 3 o'clock, or 6:15. The angle between the hands stays the same, but
because they point to different places in space, they indicate a different time. The
position of the carbon-oxygen bond is like the fixed angle of the clock hands, but
pointing to different places on the clock face.
When more than one Lewis structure can be drawn, the molecule or ion is said to
have resonance. The individual Lewis structures are termed contributing
resonance structures. Resonance is a common feature of many molecules and
ions of interest in organic chemistry.
Which one of these three structures is the correct one? How could we tell? If
structure A was correct, laboratory measurements would show one shorter bond
(the carbon-oxygen double bond) and two longer bonds (the carbon-oxygen single
bonds). Measurement of structures B and C would give the same results as well.
As it turns out, laboratory measurements show that all three bonds are equal and
between single and double bond length. This suggests that none of the Lewis
structures we have drawn are correct. It further suggests that the actual structure
has three equal carbon-oxygen bonds that are intermediate between single and
double bonds.
Perhaps the three Lewis structures for carbonate ion are in rapid equilibrium. The
structures are changing so quickly that all we see can measure is an average blur
(structure D), instead of being able to detect individual structures. By analogy,
consider a camera with the shutter left open. The picture would be a blur that
looks like A, B and C all at the same time. Structures A, B and C have the same
bonds and electron distribution, the only difference is the position of the bond.
Thus the three structures have equal stability, and the three structures would occur
to the same extent at equilibrium. The blur we see would look like 1/3 A,
1/3 B and 1/3C. The bond lengths would be a blur as well; we would perceive
them as being something between single and double bonds. The charge would
shift so rapidly that we would see it on all oxygen atoms at once. Since each
oxygen atom has a 1- charge in two of the three equilibrium contributors, each
oxygen atom would appear to have, on average, a charge of 2/3-.
Because electrons are shifting around, the formal charge distribution will vary
between resonance structures. The formal charge of an atom that gains a pair of
electrons through resonance becomes one unit more negative. Conversely, the
formal charge of an atom that shares a pair of electrons that it did not share
previously becomes one unit more positive.
The rule is violated because structure E has 12 valence electrons (four bonding
pairs and two lone pairs), whereas structure F has 14 valence electrons (five
bonding pairs and two lone pairs). Therefore these cannot be resonance structures
of the same ion. (Structure F also violates rule 2.)
Rule 2: The octet rule must be obeyed. Hydrogen may never have more than
two valence electrons. Lithium through fluorine may never have more than eight
valence electrons. (A carbon with five attachments, often called a "pentavalent
carbon" has ten valence electrons. This is forbidden because carbon does not have
the space in its orbitals to accommodate ten electrons. You should take care to
avoid this common mistake made by inexperienced organic chemistry students.)
Certain elements commonly encountered in organic chemistry may have ten
valance electrons. These elements are in periods three and higher in the periodic
table, and include chlorine, bromine, iodine, phosphorus and silicon. Of all the
atoms commonly encountered in organic chemistry, only sulfur can routinely
expand its octet to include twelve valence electrons. These atoms expand their
octets so as to improve the importance of the resonance structure.
Structures I and J are both acceptable resonance contributors for bisulfate ion, the
conjugate base of sulfuric acid. The sulfur atom of structure J has 12 valence
electrons, an expanded octet. Sulfur is a third row element, so an expanded octet is
allowed. Structure J is the more important resonance structure because it
maximizes the number of covalent bonds and minimizes the number atoms with a
nonzero formal charge.
Structures K and L are both acceptable Lewis structures, but they are not related
by resonance because the circled hydrogen atom has changed position in space.
Exercises: Draw all reasonable resonance forms for the structures shown below.
Use curved arrows to indicate electron pair changes.
Resonance: Most Important Resonance Contributor
The carbon of structure A has an open octet. All the atoms of structure B have full
octets. Therefore contributor B is more important than contributor A, despite the
fact that the positive charge is on the more electronegative oxygen atom instead of
the less electronegative carbon atom.
Preference 2: If a resonance contributor must have formal charge, the most
importnat contributor has these charge(s) on the atoms most willing to
accommodate them. Negative charges are best accommodated on more
electronegative atoms, whereas positive charges are best accommodated on the
least electronegative atoms.
Preference 4: The most significant contributor will have the least number of
formal charges.
Exercises: Determine the most significant resonance contributor for each set
of contributing resonance structures drawn previously.
Stereochemistry: Vocabulary
Exercise Solutions
Meso compound: A compound that has at least two stereocenters but is achiral.
Plane polarized light: Light in which the electric field component oscillates in a
single plane.
Stereocenter: An atom that has four different groups attached to it. (Not limited to
just carbon.)
Stereoisomer: One of a set of isomers that have the same connectivity of atoms,
but differ in the position of the atoms in space. Stereoisomers cannot be
interconverted by rotation around a single bond. (Conformational isomers are not
stereoisomers.)
Solution 1:
a. When looking for stereocenters, pay careful attention to the "four different
attachments" criterion. Recall that hydrogens of "stick structures" are usually not
drawn. Also note attachments that differ only in conformation do not make a
stereocenter. The only carbon of 2-butanol that bears 4 different attachments is the
alcohol carbon.
Chiral molecules are nonsuperposable with their mirror images. This can be tested
on paper or with molecular models using the two methods described below.
Internal mirror plane. We can look for a plane of symmetry in the molecule.
Imagine this plane as a mirror through the middle of the molecule. If one half of
the molecule is reflected into the other half, then the molecule is achiral. If no such
mirror plane exist, the molecule is usually chiral. (There are symmetry elements
other than a mirror plane that may render a molecule achiral, but these are rarely
encountered and thus beyond the scope of an introductory organic chemistry
course.) Molecular models can be used in the same way.
Example 1: Using the method of an internal mirror plane, determine if
cyclohexanol is chiral or achiral.
Solution 1: To determine if cyclohexanol is chiral using the internal mirror
method, draw a mirror plane through the middle of molecule. If there are any
unique functional groups or atoms within the molecule, these must lie within the
mirror plane, so that one half of the atom or functional group is reflected into the
other half. In this case, there is only one alcohol functional group, so it must be
contained in the mirror plane. Figure 1 shows that the mirror plane bisects the
molecule into two equivalent halves, so cyclohexanol is achiral.
Figure 1. Two views of cyclohexanol showing the internal mirror plane. The
mirror plane is indicated by the dashed line.
Solution 2:
Figure 3. Left: Molecular model of cyclopentanol and its mirror image. Right: A
top view showing that these cyclopentanol models can be aligned (superposed), so
cyclopentanol is achiral.
Figure 4. Left: Molecular model of 2-chlorobutane and its mirror image. Right:
The same models stacked. The Cl-C-H portions of the models can be made to
superpose, but at the same time the methyl and ethyl groups do not. The 2-
chlorobutane models cannot be superposed, so the molecule is chiral.
Exercises: Using either method discussed above, determine if the molecules shown
below are chiral or achiral.
a. 3-Methylhexane:
This molecule is chiral because the mirror images are not superposable. The case
is very much like 2-chlorobutane, except the molecule has a propyl group instead
of a chlorine atom. Each molecule has a single stereocenter. Examination of other
molecules with single stereocenters should rapidly convince you that molecules
with a single stereocenter are always chiral.
b. Benzene:
Benzene is achiral because it has many internal mirror planes. Perhaps the most
obvious of these is the molecular plane that contains all twelve atoms.
c. Cyclohexane:
Cyclohexane can exist in many different conformations (chair, boat, etc.). In cases
of conformationally fluxional molecules, if there is one conformation that is
achiral, then the molecule as a whole is achiral. The chair conformation has a
mirror plane through the middle of the ring, containing C1 and C4, so this
conformation is achiral. Because the chair conformation is achiral, we consider
cyclohexane to be an achiral molecule.
This molecule contains no mirror planes, and mirror image molecular models are
not superposable. Therefore this molecule is chiral.
This molecule has two stereocenters, so at first guess, it might appear to be chiral.
However, it has an internal mirror plane:
This is a meso compound, and is achiral, as are all meso compounds. Note that for
a compound to be meso, the pairs of stereocenters must have the same groups
attached to them.
At first glance, we might suspect this to be a meso compound because the two
stereocenters have the same attachments. However, rotation around the bond that
attaches the stereocenters reveals that they are not reflected by an internal mirror
plane:
Careful examination will reveal that this molecule has no conformations with an
internal mirror plane and so it is chiral.
In the quest for an internal mirror plane, rotation around the bond connecting the
two stereocenters reveals the molecule to be meso and therefore achiral:
Stereochemistry: Drawing Enantiomers and Diastereomers
Discussion: For the same reasons as it is important to recognize and
classify stereoisomers it is valuable to be able to
draw enantiomers and diastereomers as well.
Drawing enantiomers: Recall that enantiomers are molecules which are
nonsuperposable mirror images. Because these are mirror image molecules, and
because stereoisomers can only have two absolute configurations, all
the stereocenters of one enantiomer will be the mirror image of the other
enantiomer. A mirror image stereocenter can be draw by switching the place of two
groups attached to that stereocenter. We can also draw the mirror image of the
enantiomer, using an imaginary mirror.
Example 1: Draw the enantiomer of (R)-2-chlorobutane shown below.
Solution 1: Let's switch the places of the methyl and ethyl groups. This gives us
(S)-2-chlorobutane. (You should label the stereocenter as R or S to verify this.)
Solution 2: Let's use the mirror image technique for this example. Once again, you
may wish to verify the answer by labeling the stereocenters of the mirror image
molecule as R or S.
Drawing diastereomers: Recall that stereoisomers differ in the position of the
atoms in space, and that diastereomers are stereoisomers that are not enantiomers.
Some thought on this will suggest that we can draw the diastereomer of a given
structure by inverting one or more, but not all of the stereocenters.
(In this particular case, the new diastereomers are meso compounds, and are
identical. This happens when the two stereocenters have the same attachments.)
Armed with these facts, and some basic concepts from general chemistry, we can
perform just about any sort of simple calculation involving optical activity and
enantiomeric composition of a sample.
Exercises:
a. Calculate the specific rotation of (2R, 3R)-tartaric acid based on the following
observation: A 0.856 g sample of the pure acid was diluted to 10.0 mL with water
and placed in a 1.00 dm polarimeter tube. The observed rotation using the 589 nm
line of a sodium lamp at 20.0 oC was + 1.06o.
b. What is the expected observed rotation of a 1.0 x 10-4 M methanol solution of
the potent anticancer drug paclitaxel (also called taxol)? [α]D20 = -49o (c = 1,
CH3OH). Paclitaxel has a molecular weight of 853.93 g mole-1.
c. A certain compound has a specific rotation of -43.2o (c = 5, toluene). What is the
observed rotation of a sample of 1.24 g of the enantiomer of this compound when
diluted to a concentration of 1.00 g ml-1 in the same solvent?
d. In his classic studies of stereochemistry and optical activity in organic
compounds, Pasteur measured the optical activity of many solutions. For the
naturally occurring enantiomer of tartaric acid, [α]D20 = +12.4o (c = 20, H2O). What
can be concluded about the ratio of tartaric acid enantiomers present in the solution
if the observed rotation is (i) -6.0o, or (ii) 0o?
b. [α]λT = α/lc
c = 0.0001 M = 0.0001 moles L-1 = (0.0001) (853.93 g mole-1) (0.001 L) = 0.00085
g ml-1
Assume l = 1.0 dm (standard polarimeter tube)
Solving for α: α = [α]λTlc = (-49o) (1.0 dm) (0.00085 g ml-1) = -0.042o.
c. Solutions of enantiomers of equal concentrations rotate plane polarized light to
an equal extent but in opposite directions. If a certain compound has a specific
rotation of -43.2o (c = 5, toluene) then the enantiomer has a specific rotation of
+43.2o (c = 5, toluene). From the previous question,
α = [α]λTlc = (+43.2o) (1.00 dm) (1.00 g ml-1) = +43.2o. We could have anticipated
this result without doing a calculation, as the rotation is observed under the
"standard conditions" of 1.00 dm tube and 1.00 g ml-1 concentration.
d. i) If the sample is levorotatory, then the concentration of the (-) enantiomer is
greater than the concentration of the (+) enantiomer. We cannot calculate the exact
concentration, as we do not know how much (-) enantiomer is being canceled by
the (+) enantiomer. For example, the sample might contain 1.1 g ml-1 of the (-)
enantiomer and 1.0 g ml-1 of the (+) enantiomer. This solution would have the
same rotation as a 0.1 g ml-1 solution of the (-) enantiomer alone.
ii) Enantiomers have equal but opposite rotations. An observed rotation of zero
implies the enantiomers are present in equal concentrations (a racemic mixture).