CHE169 - Exp # 8
CHE169 - Exp # 8
CHE169 - Exp # 8
29 DEC 2009
LC CHE 169
Exp. # 8
THE MOLAR VOLUME
OF A GAS
1. Introduction.
The molar volume of a gas is the volume or space occupied by one mole (or an Avogadro's number
of molecules) of that gas. An ideal, or perfect, gas occupies a volume of 22.414 liters (cubic decimeters)
per mole when the gas is at standard temperature and standard pressure (STP) conditions – 273.15 K
and 1.00 atm. Real gases, which do not behave exactly ideally, will generally have molar volume values
that are not the same as that for ideal gas under the same conditions. For example, the molar volume of
carbon dioxide is found experimentally to be 22.429 L/mol at STP while the molar volume for molecular
oxygen under the same conditions is 22.392 L/mol. As can be seen, even these simple gases show
deviations from ideal gas behavior, though the deviations are relatively small, less than 1% (+0.07% and
0.010% respectively). More complex molecules, especially those exhibiting hydrogen bonding, show
larger deviations, sometimes as much as 5 to 10% or more.
In this experiment, the molar volume of hydrogen gas will be determined at room conditions. The
volume of the hydrogen collected will then be converted to the volume the gas would occupy under STP
conditions using the laws of Boyle and Charles. This STP volume for the sample will then be used to
calculate the molar volume of the gas at STP. This result is then compared with the molar volume for an
ideal gas and with the known molar volume for this gas. (Note: It is important not to use the ideal gas law
for these calculations since it assumes ideal behavior, and thus has the ideal gas value of the molar
volume “built in.” Can you specify how it is build in?)
Hydrogen gas will be generated by reacting completely a known amount of magnesium, an active
metal, with concentrated hydrochloric acid. The gas that is evolved will be collected by displacement of
water using a graduated tube, called a eudiometer (tube), which allows the direct measurement of the
volume of the gas at room temperature. The partial pressure of the hydrogen gas in the tube will be
calculated by applying Dalton's Law to the mixture of hydrogen gas and water vapor actually present in
the collection tube.
2. Procedure.
Obtain a eudiometer and rinse it well. Select either a preweighed sample of magnesium ribbon or
cut a piece of magnesium ribbon that weighs between 70 and 80 mg (maximum mass 85 mg) and weigh it
to the nearest 0.1 mg (0.0001 g). Compress the ribbon into a small, compact bundle and wrap it
completely with a 20-25 cm piece of thin copper wire, leaving a tail of about 5 cm (the magnesium should
not be visible through the wire “cage.” Add about 20 mL of conc. HCl (aq) to the eudiometer, then finish
filling the tube completely with deionized water, being careful to minimize the mixing of the acid and
water. Insert the metal sample into the tube to a depth of about 5 cm holding the tail of the wire in place
against the side of the tube with a rubber stopper having one or two holes. Top off the tube/stopper with
water and covering the hole(s) in the stopper with your finger, invert the tube into a 600-mL beaker
containing deionized water (no more than 475 mL). Clamp the tube in a vertical position. The acid will
diffuse down the tube and as it reaches the magnesium, hydrogen gas should begin to form. (How will
you know) Watch carefully as the gas evolves, and if any small pieces of magnesium break loose and float
to the surface, be sure they do not stick to the walls of the eudiometer above the level of the solution.
Should this occur, the weighed magnesium sample will not be completely converted to hydrogen gas and
the run must be discarded.
After all the metal has reacted, gently tap the tube to release any bubbles of hydrogen gas adhering
to the sides. When the tube is at room temperature, read the volume of the gas to the nearest 0.1 mL.
Measure the temperature of the gas (air near the eudiometer tube) and of the water in the beaker, both to
the nearest 0.1oC. Measure the height of the water in the beaker and in the tube to the nearest 1 mm.
Read and record the barometric pressure to the nearest 0.1 mm Hg.
The partial pressure of the hydrogen gas in the eudiometer must be determined in order to convert
the measured volume to the volume of dry (pure) hydrgoen at STP. At the end of the experiment, the
eudiometer contains hydrogen gas, water vapor and a column of liquid water, all of which contribute to
the pressure which just counterbalances the opposing the external (atmospheric) pressure exerted at the
surface of the water in the beaker. Therefore, using Dalton’s law, we can write
The volume of dry hydrogen at STP is calculated by applying the laws of Boyle and Charles to the
measured gas volume using the temperature of the gas and the calculated value of the partial pressure of
hydrogen, phydrogen(g). The number of moles of hydrogen generated is calculated from the amount of
magnesium reacted using the stoichiometry of the reaction. The molar volume of the hydrogen at STP is
the ratio of these two values.
TABLE: VAPOR PRESSURE OF WATER
Temperature, oC p, mm Hg
15.0 12.79
20.0 17.54
25.0 23.76
30.0 31.82
35.0 42.18
If values between those listed in a tabulation of two variables that depend on one another in a
systematic way can often be found to a reasonable accuracy using numerical interpolation or by graphing
the data and reading (interpolating) intermediate values from the graph. In this experiment, you will use
both of these methods to obtain the vapor pressure of water at the temperature of your experiment.
The numerical interpolation method assumes that the variables, temperature and vapor pressure in
this case, are linearly related between adjacent entries in the table. To do a numerical interpolation based
on this assumption, the rate of change of one variable with respect to the other (here the rate of change of
pressure with temperature) is calculated from the two adjacent entries in the table that “bracket” the
desired value. This “rate” value (or slope for the straight-line dependence assumed to exist between the
two “data points”) is then used to calculate the amount above the lower bracketing table value the desired
value is. This amount is then added to the lower of the two bracketing values to obtain the desired value.
In the graphical method, the desired value is found by plotting the known values of the variables
against one another, fitting a smooth curve to the data points, then “reading” (interpolating) the desired
value from the graph.
In the example below, these two methods are applied to the case where the vapor pressure of water
at 18.6 oC is desired.
Start by finding the values in the table above that bracket the desired temperature and take the
difference in the values of these two variables. In this example, the values bracketing 18.6 oC are 15.0 oC
and 20.0 oC, giving
Now take the ratio of the difference in vapor pressure to the difference in temperature:
NOTE: The value of 0.95 mm Hg/oC used above is valid only for the temperature range between 15
and 20oC. If your data is in any other temperature range, the proper value of the rate/slope
for that temperature interval must be calculated.
To illustrate the numerical interpolation method, we present a “long approach” which hopefully
more clearly illustrates the method, followed by a “short approach” which you may prefer to use when you
do your work.
Long Approach We use the rate/slope just calculated to construct an expanded table showing the p
values for 1 oC intervals:
15.0oC 12.79 mm Hg
18.6oC ? mm Hg
20.0oC 17.54 mm Hg
It should be obvious that the desired value for pwater(g) corresponding to 18.6oC will be between 15.64 and
16.59 mm Hg. In fact, it will be
of the interval between 18.0 and 19.0oC. Thus the desired value is (0.6 x 0.95) above the lower
bracketing value and is given by
In these cases, it is assumed that the same precision possessed by the values in the table can be retained
when reporting interpolated values. The expanded table was constructed here to more clearly illustrate the
process; one need not make such a table to obtain one value.
Short Approach To obtain a single value, first take the difference between the desired temperature
and the lower value of the bracketing values:
Then, since the vapor pressure increases by 0.95 mm Hg for each degree increase over 15.0 oC but under
20.0 oC (as calculated above), the vapor pressure will be greater than 12.79 mm Hg by
(Note: Two decimal places are kept to match the precision of the tabulated data.) The vapor pressure at
18.6 oC will thus be
Note that this is the same value as was found using the longer method.
GRAPHICAL METHOD.
To use this method, a graph of the appropriate variables must be prepared. In this case, a plot of
p vs. t could be used (see Fig. A). However, in the case of vapor pressure vs temperature, a plot of log
p vs. 1/T (see Fig. B) is preferred because the resulting plot is usually nearly linear. A linear plot is
desirable because it is easier to draw the best line to “fit” the data – and it is easier to read. [Note that “t”
is used represents temperature on the Celsius scale and “T” temperature on the absolute scale.] See
Experiment #1: Graphs and Graphing for guidance on how to construct a graph.
1.7
log(vapor pressure)
45
40 1.6
35 1.5
30 1.4
25 1.3
20 1.2
15
1.1
10
15 20 25 30 35 0.0032
0.00325
0.0033
0.00335
0.0034
0.00345
0.0035
Celsius Temperature 1/T
1. Once the graph is plotted, take the temperature at which you wish to determine the vapor
pressure and find either the value of the Celsius temperature if using Fig. A or the reciprocal of
the absolute temperature if using Fig. B on the abscissa or horizontal axis. Draw a (sharp) line
perpindicular to the axis at this point until it intersects with the experimental curve. At the
point of intersection, with the curve, draw a (sharp) line perpendicular to the ordinate or
vertical axis. Read the value on the ordinate. If you are using Fig. A, this is the value of the
vapor pressure; if you are using Fig. B, this value is the log p and you must calculate p by
taking the antilog of this value.
Revision 1.0.2. 29 DEC 2009
CHE 169
LC Exp. # 8
MOLECULAR:
TOTAL IONIC:
NET IONIC:
1. (b) If 0.050 mol magnesium metal reacts with HCl(aq), how many moles of hydrogen gas are
formed? Assume hydrogen to be an ideal gas.
2. Using the definitions for decimeter (dm), centimeter (cm), and milliliter (mL), show that one-
3
liter (L) is the same as one cubic decimeter (dm ).
3. Using the vapor pressure data on page 2 of the Introduction, plot a graph of the log of the vapor
pressure of water, log p, on the ordinate against the reciprocal of the absolute temperature, 1/T,
on the abcissa. Follow the guidelines in Experiment #1.
o
4. Determine the vapor pressure of water at 22.2 C using
(a) Numberical interpolation
(b) Graphical method
(c) Compare the values obtained by the two methods
5. The density of hydrogen gas, H2(g), at STP has been measured to be 0.08988 g/L.
(a) Calculate the molar volume of this gas at STP.
(b) Calculate the per cent deviation of this value from the molar volume of an ideal gas,
22.414 L.
(c) Assuming Charles’ law to be valid, calculate the molar volume of this gas at 1.000 atm and
o
25.00 C.
(d) Assuming the molecules of the gas “occupy” equal fractions of the total gas volume, and that
the sum of the volumes “occupied” (assigned) to each molecule equals the total volume of
the container, calculate the average volume “occupied by’ (associated with) a single molecule
of this gas at STP. (Note that this average “occupied” volume includes both the volume
actually physically occupied by a molecule of hydrogen plus the fraction of the “dead” --
actually empty -- volume in the container associated with (assigned to) it.)
(b) Determine the percentage of the total “occupied” volume per molecule at STP (as calculated
in 5(d)) that is actually occupied by the H2 molecule, assuming the H2 molecule can be
approximated by a sphere of diameter 130 pm. The difference between this percentage and one
hundred percent is the percentage of “dead” or empty space in the gas sample.
(c) Determine the average center-to-center distance between nearest neighbor molecules in a
sample of H2 gas at STP. (To do this calculation, it is useful to imagine the sample of gas is a
cube, which in turn is divided into smaller cubes of equal volume each with one molecule at
the center of it.)
Revision 1.0.2. 29 DEC 2009
CHE 169
LC Exp. # 8
CALCULATIONS:
SHOW COMPLETE "SET-UPS" (and the rounding off) FOR ALL CALCULATIONS on the back of this
page or on a separate sheet. Report results to the correct number of significant figures and correct units.
1 2
1. Absolute temperature of the gas
5. Moles of hydrogen
Average deviation