Melting point

1. Depending on the mode of circulation, the observed melting point could be either higher or lower than
the true melting point.
2. An insoluble impurity like charcoal should not affect the melting point.
3. Mixtures of A with B, B with C, and A with C should all show depressed melting points.
4. Too-rapid heating of the melting point bath will not allow the mercury (large heat capacity) in the
thermometer to warm up to the temperature of the sample (small heat capacity). Therefore, the sample
will appear to have a lower melting point than it actually has.
5. All compounds melt over a range of temperature under the conditions used to determine the melting
points of organic compounds.
6. The solvent remaining in contact with the crystals is an impurity and will normally depress the melting
point.
7. The melting point sample should be finely powdered to aid heat transfer throughout the sample. A
finely powdered sample has good thermal contact with the sides of the melting-point capillary.
8. The melting point will range from below 80C (the melting point of naphthalene) to about 105C.
9. Since impurities depress the melting point of pure compounds, the unknown is Compound A.
Impurities are present in the unknown because it has a melting point of about 3C.
10. It is necessary to heat the melting point bath slowly to allow time for complete transfer of heat from
the bath through the capillary to the sample.
11. To allow good heat transfer from the walls of the capillary to the crystals.
12. (a) If the sample were mixed with pure acetanilide, the melting point would remain the same.
(b) If the sample were mixed with benzoic acid (mp 122C), the melting point of the mixture would be
below that of acetanilide and the mixture would melt over a large range, perhaps 95- 105C.
13. A roughly spherical molecule such as 2-methyl-2-propanol will not have a large surface area and
therefore will not have the intermolecular van der Waals attractions that a linear molecule such as 1butanol has. Thus, the former molecule boils at 83C while the latter boils at 118C.
14. To relieve pressure built up as the system is heated.

Recrystallization
1. The gray color of the naphthalene is due to traces of decolorizing charcoal. It can be removed by
filtration through fine filter paper.
2. The amount of water required to dissolve 25 g of phthalic acid (using the solubility information in
Experiment 2) is 139 mL. On cooling to 14C, this solution should deposit 24.25 g of phthalic acid.
3. Activated carbon is added to adsorb high-molecular-weight impurities, which are often colored and
relatively less soluble.
4. Activated carbon will adsorb some of the product, decreasing the yield.
5. A mixture of solvents is used when no single solvent has the desired property of rendering the
substance soluble when hot and insoluble when cold.
6. During suction filtration of a hot solution, evaporation of the solvent takes place with attendant
evaporative cooling. The combination of these two effects causes crystals to form and clog the Bchner or
Hirsch funnel.
7. A fluted filter paper has a larger surface area through which the solvent can flow than an unfluted filter
paper, which presses against the glass side of the funnel.
8. If a long-stem funnel is used for filtration, the filtrate will cool and deposit crystals as it passes down
the stem, clogging the stem.
9. Vacuum filtration is a much more efficient method for removing solvent from the crystals than is
gravity filtration.
10. Wood applicator stick will often interact with the reagents being used in the reaction, contaminating
the product.
11. The large opening in a beaker allows solvent to evaporate too easily when trying to dissolve a solute.
A crust of impure material appears around the edge on cooling. The Erlenmeyer flask solves these
problems.

Distillation
1. There will not be much correlation. The distillation will begin at a temperature above the lower boiling
component and end below the boiling point of the higher boiling component.
2. The conclusion should be that the distillate is not pure.
3. If the experiment has been done carefully, the conclusion should be that much of the distillate consists
of a pure cyclohexane fraction and a pure toluene fraction.
4. Much of the distillate will consist of 95% ethanol and 5% water, a low-boiling azeotrope with bp
78.15C. The fact that it has a constant boiling point does not mean that it is one substance.
5. A soluble, nonvolatile substance such as sodium chloride will raise the boiling point of an aqueous
solution. An insoluble substance will have no effect.
6. Heat (of vaporization) must be added to the system to cause the water to vaporize completely.
7. This descending liquid, in a slow and careful distillation, is in equilibrium with ascending vapor. From
Figure 5.3 on page 92, we can see that the vapor is always richer in the low boiling component.
Therefore, this liquid rich in the high boiling component must return to the flask for maximum separation
of a mixture.
8. The application of heat to a cold, sealed, distillation apparatus will cause the gas in the apparatus
(primarily air) to expand and build pressure, which may cause the apparatus to come apart. A distillation
in progress can, of course, be sealed from the Copyright Cengage Learning. All rights reserved. 16
PART I Comments on Experiments atmosphere because no vapor should escape from the apparatus.
9. The equilibrium between ascending vapor and descending liquid is not established instantaneously. A
slow distillation allows time for this equilibrium to become established.
10. The packing provides a large surface area on which heat exchange and equilibrium can take place
between the descending condensed vapor (richer in the higher boiling component) and the ascending
vapor (richer in the lower boiling component).
11. The cloudiness is due to an azeotrope of water (often a contaminant) and cyclohexane, which has a
lower boiling point than pure cyclohexane. On condensation, the azeotrope separates into two phases and
then appears cloudy.
12. Boiling point is a function of pressure. Lowering the pressure over the system will lower its boiling
point. Cyclohexane and toluene can be separated at a lower pressure. The boiling point of cyclohexane
will still be lower than that of toluene.
13. If the water entered the condenser at the top it is possible for it to run down the inside of the
condenser and not make contact with the inner tube containing the hot vapors to be condensed.

Steam Distillation
1. Ignore qu 1.
2. Ignore qu 2.
3 Ignore qu 3.
4. Ignore qu 4.
5. If the steam valve is turned off before the trap is opened, the steam in the trap will condense, creating a
partial vacuum that will suck liquid from the flask into the trap and up the hose to the steam valve. If the
trap is partially opened, this process will create a siphon that will siphon all of the liquid in the flask down
the drain!
6. The ratio of moles of water to moles of toluene is equal to the ratio of the vapor pressure of water to
that of toluene in the steam distillate. A mole of toluene occupies 106 mL while a mole of water occupies
only 18 mL; hence the volume of toluene will be larger than that of water in the distillate.
7. Sublimation should have aided in the purification of the unknown as indicated by appearance (black to
white) and perhaps by melting point.
8. Some common substances that sublime: snow and ice. Clothes can be hung out to dry even when the
temperature is below 0C. Dry ice, solid carbon dioxide, sublimes to the gas without melting. Any solid
that has a strong odor is subliming; for example, moth balls (p-dichlorobenzene or, formerly,
naphthalene).
9. Foods for freeze drying are simply placed in a high vacuum chamber. The food will freeze (without
external application of cold) as the first water evaporates because of the high heat of vaporization of
water. Once all the water has evaporated, the temperature of the food will rise to room temperature. The
water that evaporates is collected on a very cold surface in order to maintain the high vacuum.
10. The difference in height between the column of mercury on the left and the one on the right would be
760 mm, atmospheric pressure.
11. Important criteria are volatility, stability to heat, ease of separation into fractions based on boiling
point, and, for steam distillation, vapor pressure and water solubility.

Extraction
1. Ignore qu 1.
2. If the stopper is not removed from the separatory funnel, very little liquid will drain from the stopcock
because a partial vacuum is created within the funnel.
3. p-Nitrophenol (Ka = 7 108, pKa = 7.15) would not be expected to dissolve in bicarbonate because it
is a weaker acid than carbonic acid (Ka = 3 10 7). 3,5-Dinitrophenol (Ka = 7.1 106, pKa = 5.15), a
stronger acid than carbonic acid, will dissolve in bicarbonate.
4. Ignore qu 4.
5. Ignore qu 5.
6. Ignore qu 6.
7. Ignore qu 7.
8. The flow diagram would look like that in Figure 7.10, except that phenol is not present, so an
extraction with strong base is not needed.
9. Ignore qu 9.
10. Acetaminophen is a phenol and thus a weak acid. It can be extracted from an organic solvent with a
strong base such as sodium hydroxide. This aqueous solution upon acidification will regenerate
acetaminophen which can be isolated by extraction into an organic solvent.
O
HN

O
CH3

HN
-

OH
H+

OH

Acetaminophen
insoluble in H2O,
weakly acidic

CH3

Ionic, soluble in water,

insoluble in ether

11. Ignore qu 11.

TLC
1. The butenes are very volatile and will evaporate before they can be detected.
2. The solvent evaporates selectively from the top of the TLC plate while the compounds being eluted
continue to travel upward. Their Rf values will be too large as a consequence.
3. The mixture being analyzed will dissolve in the elution solvent and will not travel up the TLC plate.
4. Naphthalene, a nonpolar hydrocarbon, will be at the top of the plate (have the largest Rf value) while
the highly polar butyric. PART I Comments on Experiments 27 acid will be strongly attracted to the
adsorbent and have the lowest Rf value. The ester, phenyl acetate, will be in between.
5. The spots will grow larger as the compounds diffuse in all directions. If the solvent does not evaporate
from the top of the plate (see Question 2), the Rf values should not be affected.
6. The smallest Rf value would be given by the substance most strongly adsorbed to the silica gel. This
would be the most polar substance, acetic acid. Then, in order of polarity, we might expect to see 1butanol, acetaldehyde, 2-octanone, and, finally, with the largest Rf value, decane.
7. The spots of various components will overlap to the point where the number of different components
cannot be ascertained.
8. The solvent evaporates selectively from the top of the TLC plate while the compounds being eluted
continue to travel upward. Incorrect Rf values result.
9. If a solvent of too low polarity were used, the components would stay adsorbed to the silica gel and
would not move from the starting point. If the solvent polarity were too high, the components in the
mixture would dissolve readily in the solvent and travel with the solvent front.
10. Two spots with Rf values (measured from the origin) of about 0.44 and 0.46. It is as if the
chromatogram were started anew with the spots from the first chromatogram.
11. Ibuprofen has a chiral center.
12. The solvent traveled 50.5 mm and Substance B traveled 36.5 mm, so the Rf of B is 36.5/50.5 = 0.72.

1-Bromobutane
1. n-Octyl alcohol is not miscible with water and would require vigorous stirring to complete the reaction.
t-Butyl alcohol will react with hydrobromic acid almost instantly at room temperature to form t-butyl
bromide through the intervention of the easily formed tertiary carbocation.
2. Lack of complete reaction will leave unreacted n-butyl alcohol, dehydration will give 1-butene, and a
competing reaction will give di-n-butyl ether.
Each of the above impurities protonates in concentrated H2SO4 to give the acid-soluble oxonium or
carbonium ions and will be removed with the acid. n-Butyl bromide does not accept a proton.
3. Sodium bromide should be replaced by sodium chloride and the reaction time and temperature
increased slightly.
4. H2O + HSO3 + Br2 2Br + SO4 2 + 3H+
5. The rate of a reaction approximately doubles for each 10C rise in temperature. Therefore, heat is
applied to the reaction to speed it up. If it were heated in an open flask, both the alcohol and the bromide
would escape. The reflux condenser returns them to the reaction flask.
6. Water and n-butyl bromide cannot be separated by distillation because their boiling points are so close.
They also codistill as an azeotrope.
7.
(a)

OH

+ H

+ H+
H

(b)

+ H

O
H

..

OH
..

O
H

8. Bromide and hydroxyl groups are electron withdrawing; they decrease the electron density about the
nearby carbon, making it resonate at low field.