Daniel D.

Lee
TA: Courtney Guenther
CHEM 245-102
February 3rd, 2011

Lab Report #1
SOLIDS: Recrystallization and Melting Points

Section 4: Results and Observations

Melting Point Determination
Mel-Temp apparatus #6, Correction:

Naphthalene (Sample A):

Melting Ranges (°C)
Trial #1 78.0 – 80.0
- (-1.0) (-1.0) Mel-Temp apparatus #6 corrections
79.0 - 81.0°C Temperature Observed, corrected
Trial #2 77.0 – 80.0
- (-1.0) (-1.0) Mel-Temp apparatus #6 corrections
78.0 - 81.0°C Temperature Observed, corrected
Both trials within 1°C, ✓ (True high melting point temperature: 81°C)

Benzil (Sample C):

Melting Ranges (°C)
Trial #1 91.0 – 95.0
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
92.5 - 96.5°C Temperature Observed, corrected
Trial #2 90.0 – 95.0
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
91.5 - 96.5°C Temperature Observed, corrected
Both trials within 1°C, ✓ (True high melting point temperature: 94°C)

Cinnamic Acid (Sample D):

Melting Ranges (°C)
Trial #1 127.0 – 130.0
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
128.5 - 131.5°C Temperature Observed, corrected
Trial #2 128.0 – 130.0
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
129.5 - 131.5°C Temperature Observed, corrected
Both trials within 1°C, ✓(True high melting point temperature: 132°C)
Unknown (Sample 119):
Melting Ranges (°C)
Trial #1 147.0 – 149.0
(Preliminary - (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
) 148.5 - 150.5°C Temperature Observed, corrected
Trial #2 149.0 – 151.0
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
150.5 - 152.5°C Temperature Observed, corrected
Out of the 12 possible samples and according to their given upper
end of melting ranges, the observed melting point range of the
unknown can either be adipid acid or benzenesulfonamide since
their upper end of melting point range is around 150°C.

Mixture-melting point determinations with adipid acid (Sample N) and

benzenesulfonamide (Sample O):
Melting Ranges (°C)
Sample N 128.0 – 135.5
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
129.5 - 137.0°C Temperature Observed, corrected
Sample O 149.0 – 151.5
- (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
150.5 - 153.0°C Temperature Observed, corrected
The melting point range of the mixed sample of vial O and the
unknown reflects the initial melting point measurement of the
unknown.

Recrystallization
Benzoic acid
Initial Weight 0.90 g
Product Weight 0.23 g
Percent Weight of pure crystals recovered
Recovery
Percent Recovery = ( Weight of original sample ) × 100
Benzoic Acid:
(0.23g/0.90g)x100 = 25.56 %
Melting Point 112.0 – 116.0
Range - (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
113.5 - 117.5°C Temperature Observed, corrected
- (when heating the impure benzoic acid with the necessary solution, the
sample boiled out of the flask because the heat was set too high) – potentially
sample was lost
- After heating, the solution turns gray/dark.
- As the sample cools down, it solidifies pretty quickly into white powdery
figures
Acetanilide
Initial Weight 2.06 g
Product Weight 0.84 g
Percent
Recovery
Percent Recovery = ( Weight of pure crystals recovered
Weight of original sample )× 100
Benzoic Acid:
(0.84g/2.06g)x100 = 40.78 %
Melting Point 107.0 – 113.0
Range - (-1.5) (-1.5) Mel-Temp apparatus #6 corrections
108.5 - 114.5°C Temperature Observed, corrected
- When added to boiling water, the resulting sample is a very clear blue
solution.
- Weight of decolorizing carbon: 0.23g
o Turned the solution black, and after hot filtration the solution became
clear.
- The product was clear/white powdery crystals.

Thermometer Calibration
Temperature Observed from Iced Water 1.0°C

Temperature Observed from Boiling Water 98.0°C

Barometer Reading 757.8 mm Hg

Corrections At 0°C, -1°C

At 100°C, +2°C

Section 5: Conclusions
Melting Point Determination
In obtaining the melting points of naphthalene, benzil, and cinnamic acid, I
was able to practice using the Mel-Temp apparatus. For the observed melting
ranges, they were close to that of the true temperature ranges: the naphthalene’s
two trials’ observed upper melting point matched that of the true value’s, the
benzil’s two trials’ both showed high melting temperature 2.5°C greater than the
true temperature, and cinnamic acids’ both trials showed values that were 0.5°C less
than that of the true values. For each case, the measured values were relatively close
to the true values, and both trials for each compound were less than 1°C off each
other. Because the measured values were greater than the actual melting point
range for the benzil, less than for the cinnamic acid, and same for naphthalene, we
cannot conclude that the correction for the Melt-Temp apparatus is incorrect;
rather, it is possible that determining when melting actually ended for each
compound, the vague visual cues, may have been the cause for the small deviations.
Measuring the melting range for Unknown 119, the melting ranges came out
to be 148.5-150.5°C and 150.5-152.5°C, reflecting the upper end of melting ranges of
adipic acid and benzenesulfonamide, 150°C and 151 respectively, and indicating
that the unknown sample be one of them. Then, with the mixture-melting point
process, for which the two possible samples were each mixed with the unknown in
approximately equal proportions to get the melting ranges of the mixed samples, the
melting range of adipid acid and the unknown was 129.5-137.0°C, less than when
the unknown was measured previously. On the other hand, the mix of the
benzenesulfonamide and the unknown had a melting range (150.5-153.0°C) that
was consistent with the unknown’s individual measurement. Therefore, it can be
concluded that the unknown sample 119 was benzenesulfonamide since is it
generally the case that impurity decreases the melting point of a pure solid.

Recrystallization
For recrystallizing the impure benzoic acid, the product weight was 0.23 g
while the initial weight was 0.90 g. The percent recovery was 25.56% ad the melting
range of the product was 113.5-117.5°C. As for the percent recovery, if it is less than
around 20%, the experiment is considered unsuccessful, having lost too much of the
desired sample during the process. Even though 25.56% is not within this
unfavorable range, it is still pretty close to it. This may have been due to products
lost during filtrations or may have been due to it spilling over when it was boiling at
the beginning of the experiment. Also, considering how the true upper melting range
of benzoic acid is 122°C, the observed 113.5-117.5°C range is pretty low. This may
have also been due to the filtration process that was not able to completely purify
the sample. The hot gravity filtration process may have let some impure solutes to
pass the filter paper, possibly due to improper folding of the fluted filter paper or
maybe the crystallized sample was not cleanly washed enough with cold solvent
right after the vacuum filtration to wash away the soluble impurities that may have
been with the wetness of the product.
As for the acetanilide, the initial weight of the sample was 2.06g and the
product weight was 0.84g. The percent recovery was 40.78% and the melting range
of the product was 108.5-114.5°C. The percent recovery of the experiment indicates
that a fair amount of the original sample was able to recrystallize and to purify to
become products. Also, compared to the true upper melting range of acetanilide of
114.3°C with the observed 108.5-114.5°C, the two upper melting range is very close.
However, the range of the observed is a bit too large, which is far greater than the
ideal 2°C range, indicating some sort of impurity or error in measurement of the
melting range via the Mel-Temp apparatus.
As for the thermometer calibration, if the temperature from this specific
thermometer is observed to be 1°C, then subtract 1°C to correct it because the actual
temperature is probably 0°C. If the temperature is observed to be 98°C, add 2°C to
correct it because the actual temperature is probably 100°C. Technically speaking,
to get the actual temperature, at 0°C, subtract 1; at 100°C, subtract -2.

Section 6: Answers to Assigned Questions

Exercise 20) For the benzoic acid, 0.9 grams of benzoic acid was recrystallized from
20 mL of water. With solubility of 0.02 g per 100 mL at 0°C, we expect 0.004 g to be
the amount of unrecoverable by virtue of its solubility at 0°C. For the acetanilide,
2.06 grams of acetanilide was recrystallized from 40 mL of water. With solubility of
0.53 g per 100 mL at 0°C, we expect 0.212 g to be the amount of unrecoverable by
virtue of its solubility at 0°C.
Calculations for benzoic acid: 0.02g/100mL = x g/20mL
Calculations for acetanilide: 0.53g/100mL = x g/40mL

Exercise 23)
a) In the solution step, an unnecessarily large volume of solvent is used.
a. Using excessive amounts of solvent decreases the recovery of the
solute because it will waste time in boiling off later in the process and
if too much solvent is used for cooling later on after filtration, little or
no solutes crystallizes out. More solvent means more of the solutes
will stay dissolved.
b) The crystals obtained after filtration are not washed with fresh cold solvent
before drying.
a. The extra fresh cold solvent will allow for the sample to become purer
by washing away the soluble impurities that may be present after
filtration because the crystals are not completely dry yet. After boiling
off, the crystals may still have solvent or water pockets that were able
to stay with the crystals, which would have soluble impurities that
need to be washed with fresh cold solvent before drying.
c) The crystals referred to in (b) are washed with fresh hot solvent.
a. If the crystals are washed with fresh hot solvent, the crystals are in
danger of being dissolved again, eventually leading to a lost of the
desired product.
d) A large quantity of decolorizing carbon is used.
a. Even though it is able to suck up impurities, it will also absorb some of
the desired products if too much of the decolorizing carbon is used.
e) Crystals are obtained by breaking up the solidified mass of an oil that
originally separated from the hot solution.
a. That oil will probably contain some impurities. When the separated
oil cool down, the oil crystallizes; however, because the oil was part of
the solution before separating, it is likely that the oil dissolved some
of the solvent and impurities there within. Therefore, obtaining
crystals from breaking up the solidified mass of an oil that originally
separated from the hot solution is not preferable.
f) Crystallization is accelerated by immediately placing the flask of hot solution
in an ice-water bath.
a. If the hot flask is immediately placed in an ice-water bath, the flask
may shatter. Also, if the solution is not cooled slowly, it may result in
rapid recrystallization of small crystals that may trap impurities.

Exercise 14)
a) Melting range of about 2°C is considered normal and pure.
 b) Because the sample decomposed while melting, it is inferred that the sample
is impure. Therefore, the melting point is lowered as a result. In this case, the
147°C (dec) not only is not in the format of melting ranges, it is also
decomposition while melting, indicating some sort of impurity.
c) 46-60°C melting range would be considered very impure as the range of 14°C
is far greater than the ideal 2°C range.
d) 162.5-163.5°C melting range indicates a pure sample as the range is only
within 1°C, unless it is a mixed sample at its eutectic point which is a rare
phenomenon.

Exercise 16)
Mixture-melting point procedure will use the pure samples to identify the unknown.
By mixing the pure samples of the three possibilities with the unknown in equal
proportions, the melting ranges of the mixed samples will be measured using the
Mel-Temp apparatus. The sample that again results in the melting range around
160°C will indicate that the unknown is the same as the sample mixed with it in the
mixture. The other two samples will probably have melting ranges that are less than
the previously observed 160°C.