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EXERCISE 1

MOLECULAR WEIGHT DETERMINATION


BY VAPOR-DENSITY METHOD

CHEM 111.1 – 7L
GROUP 2

GUERRERO, MARY JUSTINE A.


MARQUEZ, RENNARD
PRUDENCIO, DANIEL ANDRE
QUITAIN, CINJALEE
SANGALANG, MARIANE FRANCES

DATE PERFORMED:
JANUARY 26, 2018
DATE SUBMITTED:
FEBRUARY 2, 2017

SUBMITTED TO: SIR PAUL LLOYDSON J. ALVAREZ


I. Introduction
The ideal gas law is the combination of the relationships of the different gas laws. It is
regarded to as the equation of state for gases, wherein the condition of the gas at a certain time
is the state of the gas (Zumdahl, 2007). The ideal gas equation is defined as:
𝑃𝑉 = 𝑛𝑅𝑇 (eq. 1-1)

where P is the barometric pressure, V is the volume of the container, n is the number of moles, R
is the combined proportionality constant referred to as the universal gas constant, and T as
absolute temperature.
The ideal gas law is used as an approximation that aids us in the prediction of the behavior
of real gases. Since there are only minimal errors that result from assuming ideal behavior, the
ideal gas equation is manipulated to determine the molecular weight of volatile substances
(Zumdahl, 2007). The derived equation for the calculation of the molecular weight is defined as:
𝑚𝑅𝑇
𝑀= (eq. 1-2)
𝑃𝑉

where M is the molecular weight and m is the mass of the vapor in the container.
A common technique used in determining the molecular weight of a substance is through
the vapor-density methods. It is done by vaporizing the substance to fill a known volume at a
specific pressure and temperature. There are many methods that have been designed for the
determination of the molecular weight such as Dumas bulb method, Victor Meyer method, and
temperature-monitored vapor-density method. All these methods assume that the vapor is an
ideal gas.
In the Dumas bulb method, an unknown volatile substance is heated in a vessel of known
volume. When the last drop of the liquid evaporates, the Schlieren jet disappears. In this
procedure, mass of the vaporized liquid and the volume of the container is measured. It is
assumed that the vapor pressure inside the flask is equal to the external atmospheric pressure
and the temperature of the gas is the same as the temperature of the boiling water bath (Carolina
Biological Supply Company, 2010).
The Victor Meyer method is used for the determination of the molecular weight of a volatile
substance with known mass. The substance is volatilized in a vessel maintained at constant high
temperature. The air displaced from the vessel is cooled to room temperature, and its volume
carefully measured (Hicks-Bruun, na).
In this experiment, the temperature-monitored vapor-density (TMVD) method is applied.
It is an improved molecular weight determination method since the moment of complete
evaporation is directly identified and an exact measurement of the vapor temperature can be
obtained at the time of removal from the water bath for weighing (Grider, 1988).
Since precision and accuracy are not well defined in experimental mass determination, it
causes a major problem for vapor-density methods. The assumption that the mass of the vapor
is the mass solely measured pose a major problem in the determination of the molecular mass
(Grider, 1988).
By the end of this exercise, the students should be able to illustrate one of the many
applications of the ideal gas equation; and determine the approximate molecular weight of a
volatile substance by the TMVD method.
II. Materials and Methods
The temperature-monitored vapor density (TMVD) method was used in the experiment. A
thermometer was inserted into a small hole drilled in a Teflon plug and was secured with tape to
prevent the escape of the gas. The Teflon plug was then fitted to a 100-mL volumetric flask and
was partially submerged in a water bath. The water bath was kept in a temperature at least 10°C
above the boiling point of the sample. Figure 1.1. shows the schematic drawing of the
experimental set-up.

Thermometer
-
-
-
-
-
-
-
-
-
-

Figure 1.1. The temperature-monitored vapor density (TMVD) set up.

In the experiment, two volatile liquid samples were used which are acetone and methanol.
Primarily, the measurements of the room temperature, barometric pressure, and the relative
humidity was obtained. After this, a dry and empty 100-mL volumetric flask along with the inserted
Teflon plug and thermometer was weighed. Subsequently, the water bath was pre-heated
together with the empty volumetric flask and the assembly until the temperature reaches 2°C
above the boiling point of the sample. The dry pre-heated volumetric flask along with the Teflon
plug and thermometer was weighed while it was still hot. 0.25 mL of the sample was placed inside
the volumetric flask. It was returned to the water bath together with the inserted Teflon plug and
thermometer to continue the heating process. When the temperature of the water bath was 5°C
below the boiling point of the sample, the temperature reading of the thermometer inside the
volumetric flask was recorded at 10-sec intervals. The recording of the temperature was stopped
when the temperature reached 2°C above the boiling point of the sample (or when the inflection
point is attained). The volumetric flask together with the Teflon plug and thermometer was
removed from the set-up and was dried with a rug. It was then weighed while it was still hot. After
weighing, the volumetric flask was filled with water and weighed together with the Teflon plug and
thermometer to obtain the volume of the volumetric flask.
III. Results and Discussion
The derived ideal gas equation is defined by the relationship of the different state functions
such as corrected barometric pressure, volume of the vapor, inflection temperature, and mass of
the vapor (refer to eq. 1-2). Based on eq. 1-2, the mass of the vapor and inflection temperature
are directly proportional to the molecular weight while the corrected pressure and volume of the
vapor are inversely proportional. The parameters mentioned above were mostly obtained from
the derived equations (refer to the sample calculations) and some were gathered from using the
necessary instruments from the laboratory. It is essential to be accurate and precise as possible
to obtain the different state functions since any alteration in the values would entail a variation in
the molecular weight of the vapor.
In the start of the experiment, data on atmospheric conditions was obtained through
instrument reading and use of literature values. It was used to compute for the state functions
needed to calculate for the molecular weight of the vapor. The data is recorded on Table 1.1..

Table 1.1. Data on the atmospheric conditions.


Room temperature, °C 28
Atmospheric pressure, mmHg 747.014
Relative humidity, % 76.9
Vapor pressure, mmHg 28.349
Density, g/mL 0.996233

Then the molar mass of the moist air was computed since it is required for the calculation
of the mass of moist air. The values needed for the calculation of the molecular weight of moist
air is shown on Table 1. 2.. The corrected pressure was not accounted for, since there was no
mercury in the barometer used in reading the atmospheric pressure. Therefore, thermal
expansion did not occur. The correction of barometric pressure is vital since mercury expands
when there is a change in temperature. Hence, the temperature reading would be higher. Even
though correction reduces the errors and deviation, an accurate temperature reading cannot be
guaranteed. A more accurate reading would be obtained if a device with a direct contact inside
the flask was used to read the pressure.

Table 1.2. Computed values for the molar mass determination of moist air.
Corrected pressure (PC), mmHg 747.014
Mole fraction of water (XH2O) 0.02918336336
Mole fraction of nitrogen (XN2) 0.7669451429
Mole fraction of oxygen (XO2) 0.2038714937
Molar mass of moist air (MMma), g/mol 28.53945818

The mass of the moist air should be accounted for, since moist air is present inside the
flask. The presence of moist air can cause the decrease in the mass of the vapor. Thus, making
the molecular weight lower than the actual value should be. Hence, the value obtained for the
mass of the moist air is deducted from the mass of the flask + vapor (refer to the sample
calculations). The molecular weight of the vapor and the necessary parameters needed to
compute for it is shown on Table 1. 3..
Table 1.3. Computed values for the molar mass determination of acetone and methanol.
Acetone methanol
Trial 1 Trial 2 Trial 1 Trial 2
Volume of vapor (Vv), L 0.1041952033 0.1028188185 0.1028322692 0.1022800891
Mass of moist air (mma), g 0.1182811093 0.1167186543 0.1167339234 0.1161070953
Mass of vapor (mv), g 0.2620811093 0.3496186543 0.2650339234 0.2379070953
Inflection boiling point, °C 56.93333333 56.6 65.56666667 125
Molar mass of vapor 69.31173688 93.60563326 72.87923522 77.31401204
(mmv), g/mol

The temperature vs. time curves shown below were obtained from the temperature
reading of the vapor temperatures in 10-sec intervals (Figure 1.2-1.5). The inflection point was
determined by finding the point on the graph at which the concavity changes. The inflection boiling
point was reflected on the graphs. The temperature when the last drop of the substance was
vaporized is the inflection boiling point (Oberlerchner, 2015).

Acetone: Trial 1-
Temperature vs. Time Curve
61

60

59

58

57

56

55

54

53
0 50 100 150 200 250

Figure 1.2.: Temperature vs. time curve of acetone (Trial 1).


Acetone: Trial 2-
Temperature vs. Time Curve
58.5

58

57.5

57

56.5

56

55.5

55

54.5

54

53.5
0 50 100 150 200 250 300

Figure 1.3.: Temperature vs. time curve of acetone (Trial 2).

Methanol: Trial 1-
Temperature vs. Time Curve

68

67

66

65

64

63

62

61

60

59

58
0 50 100 150 200 250 300

Figure 1.4.: Temperature vs. time curve of methanol (Trial 1)


Methanol: Trial 2-
Temperature vs. Time Curve

68
67
66

65

64

63

62

61

60

59

58
0 50 100 150 200 250 300

Figure 1.5.: Temperature vs. time curve of methanol (Trial 2).

In the experiment, temperature-monitored vapor-density (TMVD) method was used since


minimal requirement is required and an assortment of vessels can be used. Another factor is that
it is more accurate since an exact measurement of the temperature can be obtained by using a
thermocouple probe (Grider, 1988). Unlike the Dumas bulb method where it is assumed that the
temperature of the vapor is the same as that of the water bath, abrupt changes in the temperature
can be recorded in TMVD (Carolina Biological Supply Company, 2010). Although this is one of
the most precise and accurate methods in the determination of the molecular weight, several
assumptions were made that caused errors in the computation.
Firstly, the gases were assumed to behave ideally. The ideal gas law is referred to as the
limiting law which means that real gases approach ideality at idealizing conditions (low pressure,
high temperature). There is no guarantee that the idealizing conditions were maintained
throughout the experiment. Since molecular interaction occurs in real gases, the actual pressure
and volume that were obtained are lower. However, errors and deviations can be minimized when
assuming ideal behavior if the pressure of the gases is below 1atm (Zumdahl, 2007). The ideal
gas equation can also have corresponding compressibility factors to correct for non-ideality of the
given vapor.
The second was the implicit assumption that the vapor has the same molecular weight as
the liquid. The molecular weight of the vapor is affected by the dissociation and association. A
decrease in the molecular weight is a result of dissociation while an increase is a result of
association. The increase in molecular weight is due to dimerization, the formation of dimers in
both the liquid and vapor states of a substance. It is usually exhibited by very polar substances
(Petrucci, 1997).
Another reason why it is incorrect to assume that the molecular weight of the liquid and
vapor phase are the same, is principally because of polymerization. Polymeric molecules are
generally formed from vaporization of volatile substances. Polymers are large molecules that are
composed of a single simple unit repeated many times (Umland, 1993). Since polymerization
occurs during the evaporation process, larger molecules are formed, thus, making the molecular
weight higher.
In this experiment, several errors were committed which affected the accuracy and
precision of the obtained data of the parameters. Because of this, the computation of the derived
data caused the propagation of errors and further deviation from the actual value. Instrument error
is one of the common errors done. Instrument (e.g. scales) that are not well-calibrated may have
caused an increase or decrease in the value of the parameter being measured. In the
determination of the mass of the flask, an error might have been committed if there was the
presence of small amounts of excess liquid when the flask was being weighed. This can be
prevented by ensuring the vessel is dry before weighing. Several errors committed were due to
human error. The observer may have been biased in reading the temperature and barometric
pressure. Also, a biased interpretation of the graphs may have been done when identifying the
inflection point. Making unnecessary approximations in the calculations can alter the computed
molecular weight of the sample. Another possible error is the use of impure samples. The
chemical composition of the sample may possibly be altered, thus, making the calculations
inaccurate.
The comparison between the experimental value of the molecular weight and the literature
value of the molecular mass is presented on Table 1.4. The data shows that the percent error for
both the acetone and methanol are quite large. The obtained data shows that methanol has a
higher percent error since it has undergone dimerization. Based on the molecular composition of
methanol, it has higher intermolecular forces of attraction (IMFA) and polarity. Hence, it is more
likely to form dimers and polymers, since the hydrogen in the methanol can be simply removed
and the freed oxygen can easily attach to another methanol molecule (Petrucci, 1997). In contrast,
the structure of the acetone has branches which makes the interaction of the free oxygen quite
improbable.

Table 1.4. Data for the Percent Error with respect to the literature molecular mass values
acetone methanol
Trial 1 Trial 2 Trial 1 Trial 2
Molar mass of vapor 69.31173688 93.60563326 72.87923522 77.31401204
(mmv), g/mol
Literature value of the 58.08 32.04
molecular mass, g/mol
Percent error, % 19.33838994 61.16672393 127.463281 141.3046568
IV. Summary and Conclusion
Since there are only minimal errors that result from assuming ideal behavior, the ideal gas
equation is manipulated to determine the molecular weight of volatile substances
A common technique in determining the molecular weight of a substance is through the
vapor-density methods. It is done by vaporizing a substance to fill a known volume at a specific
pressure and temperature. Although there are many methods that have been designed for the
determination of the molecular weight (such as Dumas bulb method and Victor Meyer method),
temperature-monitored vapor-density method (TMVD) was used since it is more enhanced than
the other vapor-density methods. In TMVD, the moment of complete evaporation is directly
identified an exact measurement of the vapor temperature can be obtained.
From the experiment, the obtained molar mass of acetone are 69.31173688 g/mole and
93.60563326 g/mole. If the values gathered were to be compared with the literature value that is
58.08 g/mole, the percent error would be 19.33838994 and 61.16672393% respectively.
Meanwhile, 72.87923522 g/mole and 77.31401204 g/mole were the molar masses obtained from
the methanol. In comparison with the literature value of methanol which is 32.04 g/mole, the
percent error is 127.463281 and 141.3046568% respectively. Several errors were committed
which affected the accuracy and precision of the obtained data of the parameters, thus, causing
the high percent error.
Even though TMVD is the best vapor-density method for the determination of the molecular
weight of a volatile substance, the value obtained for the molecular weight is still inaccurate since
personal and instrument error cannot be avoided. In addition, vapor density methods do not take
into consideration the molecular composition of the substances. Hence, vapor-density methods
are not the best way to determine the molecular weight of the substance. Other experimental
methods that yield less percent error can be used.
V. References
Carolina Biological Supply Company. 2010. Determination of Molar Mass by Vapor Density
Teacher’s Manual and Student Guide. Carolina Biological Supply Company. pp. 4-5.
Grider, D.J., J.D. Tobiason, F.L. Tobiason. 1988. Molecular weight determination by an improved
temperature-monitored vapor-density method. Journal of Chemical Education. Volume 65 No. 7.
pp. 641-643.
Oberlerchner, J.T., T. Rosenau and A. Potthast. 2015. Overview of Methods for the Direct Molar
Mass Determination of Cellulose. Molecules 2015, 20, pp. 10319
Perry, H., and Green A. 2008. Perry’s Chemical Engineering Handbook. 8th ed. New York:
McGraw-Hill Co.
Petrucci, R.H., and W.S. Harwood. 1997. General Chemistry Principles and Modern
Applications. 7th ed pp.504
Zumdahl, S.S. and S.A. Zumdahl. 2007. Chemistry. Seventh edition. Houghton Mifflin Company.
pp. 186-187, 492.
Table 1.2. Raw data on the masses
acetone methanol
Trial 1 Trial 2 Trial 1 Trail 2
Mass of flask at room temperature, g 87.1288 91.4718 87.1700 81.0370
Mass of preheated flask, g 87.1196 91.4654 87.1349 81.0132
Mass of flask + vapor, g 87.2634 91.6983 87.2832 81.1350
Mass of flask + water, g 190.9315 193.9033 189.6149 182.9318

Table 1.3. Temperature of heated sample in the flask at 10-second intervals.


Elapsed Temperature (°C)
time Sample: acetone Sample: methanol
(sec) Trial 1 Trial 2 Trial 1 Trial 2
0 54 54 59.7 59
10 54 54 60 59.6
20 54.5 55 60 60
30 55 55 60.5 60.4
40 55 55 60.8 60.5
50 55.4 55 61 60.8
60 55.8 55.2 61.4 61.2
70 56 55.5 61.8 61.5
80 56 56 62 61.9
90 56.5 56 62.2 62.1
100 56.8 56.1 62.8 62.5
110 57 56.1 63 62.9
120 57 56.5 63.4 63
130 57.5 56.8 63.8 63.3
140 58 56.8 64 63.6
150 58 57 64.2 64
160 58 57 64.8 64.1
170 58.2 57.1 65 64.4
180 58.5 57.1 65.2 64.8
190 59 57.1 65.5 65
200 59 57.5 66 65.4
210 59.5 57.5 66 66
220 60 57.5 66.4 66.7
230 57.5 66.8 66.9
240 58 67 67.1
250 67.2
260 67.5