(CH3)3N: BF3

Note : A continuos period of 4 to 5 hours is generally required to complete the work on the
vacuum line.

While the us of simple high vacuum systems in synthetic inorganic chemistry dates back
to the origins of chemistry, the technique as it is know today was essentially established by
Alfred Stock and His co-workers in their pioneering research on the boron hydrides in the
1920s. the volatility and extreme reactivity of these hydrides (B 2H6 spontancously burns in air)
made them particularly suitable for study in high vacuum system. Although high vacuum
techniques may be very highly specialized and sophisticated, the purpose of this experiment is
introduce only a few of those techniques that are the most fundamental and important. They are
transferring chemicals from one container to another on the vacuum line, measuring the vapor
pressure of a liquid at low temperature, and determining the molecular weight a gas.

As the name implies, vacuum lines are ussualy operated under relatively low pressures
substantially below atmospheric pressure. The unit used for expressing gaseous pressures is the
torr, and one torr is equal to mm Hg pressure. The mechanical oil pump that will be used in this
experiment to create the vacuum should be capable of reducing the pressure within the glass
apparatus to 10-3 or 10-4 torr.(It should be remembered that the vapor pressure of Hg is 1.7) x 10 -3
torr at 24oC, and any quoted pressures exclude any Hg vapor present in the apparatus. A pressure
of 10-4 torr means that the pressure exerted by other gases besides 10- 4 torr). Low pressures
accomplish two objectives. They remove any undesired reactive gases such as O 2 or H2O, and
they allow volatile substances to be rapidly transported from one portion of the apparatus to
another.

To illustrate the latter point, consider the distillation or transfer of a liquid from trap A to
B in figure 19-1. In order to make the transfer, the temperature of B must be lower than that A.
Therefore. One might immerse trab B in a dewar flask containing liquid nitrogen (b.p-196 oC).
(See Appendix 9 for other cold baths). The gaseous molecules in B will condense at this
temperature. Liquid molecules in A vaporize and diffuse by virtue of their kinetic energy to B
and are condensed. The rate of diffusion of the molecules to B depends upon the number of
collisions that they encounter on the way to B. if the system is filled with an inert gas such as He,
the diffusion of molecules from A to B is very slow because of the large number of collisions that
the diffusing molecules have with He atoms. On the ather hand, if the pressure is reduced to 10 -3
or 10-4 mm Hg, there are many fewer molecules to get in the way, and distillation occurs more
rapidly. In vacuum it is possible to make such transfers with any volatile compound. The
volatility is, of course, determined by the temperature of the liquid ; compounds having boiling
points of 150oC at atmospheric pressure may be manipulated in a vacuum system without
difficulty.
 The vacuum line be used in this experiment is shown in figure 19-4 is attached to a
mechanical, rotary vacuum pump. The oil in the pump should be of good grade and changed
regularly. After extended use the oil accumulates chemicals hanled in the vacuum line. They will
increase the vapor pressure of the oil and decrease the efficiency of the pump. Since many of
these chemicals are toxic, a tube should be attached to the exhaust port of the pump and vented
into a hood. To protect the pump from such gases, it is important that a large volume cold trap be
placed between the pump and the working portion of the vacuum line.(figure 19-4). The cold trap
is cooled with a Dewar flask containing liquid N2. While liquid N2 is sufficiently cold (-196oC) to
trap most gases used in the line. It also is cool enough to condense liquid O 2 (b.p.-183oC) into the
trap if the trap is open to air. Because liquid O2 is such a powerful oxidizing agent, it may react
explosively with any other gases thay may have also condensed into the trap. For this reason, the
cold trap should never be opened to the air until the liquid N2 trap is removed.

A vacuum line is frequently made up of several sections joined together with ground
glass joints (figure 19-4). These joints may be either of the usual standart taper type or ball and
socket joints (figure 19-2); both types are used in the apparatus in figure 17-4. The standard taper
joint is usually less likely to leak an is used where bending at the joint is not required. Where
some flexibility is needed, the ball and socket joint should be used. Both joints should be greased
with either a high vacuum silicone or kel-F grease. The latter grease will be used in this
experiment because BF3 reacts with silicone greases.

High vacuum stopcocks (figure 19-3), which may be evacuated and do not pop out even
when the pressure in the line is somewhat above atmospheric preassure, should be greased before
being used. An ungreased stopcock should never be turned; it will become scored. Since the
ground glass barel and key in a vacuum stopcock are carefully matched, it is important that these
always be kept together ; a barrel with out its matching key worthless. Since stopcocks will break
off the apparatus when put under strain and are difficult and expensive to replace, they should be
turned with both hands, one to support the barrel and the other to turn key. It is important to
realize the cost of carelessness when working with a glass vacuum system.

Although a thorough understanding of the vacuum line and its use is the most important
aspect of this experiment, a few comments should be made about the reaction that will be carried
out in the last phase of the experiment. It is a simple reaction between a gascous Lewis acid, BF 3,
and a gaseous Lewis base, (CH3)3 N, to form the solid adduct (CH3)3 N : BF3

BF3 + (CH3)3N (CH3)3N : BF3

The product, (CH3)3N : BF3, is a white solid that is stable in air and has a melting point of 146 oC.
It shows little tendency to dissociate and may even be sublimed under vacuum. The reactant,
BF3, is a colorless gas that fumes in moist air. It has a boiling point of 101 oC at 760 torr
pressure and melting point of - 127oC. Its low boiling point means that solid or liquid BF 3 may be
easily and inadvertently converted to a gas. If this occurs when the BF 3 is confined to a small
portion of the vacuum line, the pressure created by the gaseous BF 3 will easily shatter the glass
vacuum system. (If the vacuum line is designed so that it is possible to confine the gas in a small
volume of the line, a safety shield placed between the worker and the line is strongly advised.)
the other reactant, (CH3)3N, melts at 117oC and boils at 2,9oC (at 760 torr).

The simplicity of this type of reaction has lednumerous researchers to investigate the
relative acidities and basicities of numerous acid, A, and bases, B. These parameters have been
established by comparing equilibrium constants for the reaction.
K B:A
A+B:

Using different acids and bases. In some cases, it has been possible to measure Hs for the
reaction of pyridine (C5H3N) with the boron trihalides, BX3

C5H3N + BX3 C5H3N : BX3

Decrease with BX3 in the order : BBr3 > BCl3 > BF3. Thus, BBr3 forms a more stable adduct with
pyridine than does BF3. Elekctronegativity arguments suggest that BF3 would be a stronger
Lewis acid than BBr3. On closer consideration of the reaction, one notes that a considerable
reorganization of bonds occurs around boron in going from the reactant to the product. The
boron trihalides are planar molecoles, wheareas the geometry of the adducts is essentially
tetrahedral.

X X
X
B
+ C 5H 5N C5H5N B X
X X

Thus, a rehybridization of boron occurs during the reaction, and the stability of the planar BX 3
relative to the adduct is a major factor determining the H of the reaction. The planarity and
unusually short B-X bond lengths in BX3 are attributed to bonding from the p orbitals on the
halogens, X, to the empty p orbital on boron. Since the p orbitals of F are smaller and less
diffuse than those of Br, F-B p- p bonding is greater than is -bonding in the analogous Br-B
bonds. For this reason, BF3 is relatively more stable and has a lesser tendency than BBr3 to form
an adduct complex. Numerous other thermodynamic studies of adduct formation by various
Lewis acids and base have led to an understanding of many of the factors that determine the
stabilities of these complexes.

EXPERIMENTAL PROCEDURE

BF3 Should not be exposed to air at any time during the experiment, since it fumes and is
toxic. A more serious danger is one already mentioned. Namely, at temperatures above -101 oC,
BF3 is a gas ; if it is allowed to vaporize in a closed section of the vacuum line, the BF 3 pressure
will shatter the vacuum line and persons or equipment nearby. The vacuum system shown in
figure 19-4 has relatively few locations in which the BF 3 may be closed off from a mercury
manometer. If BF3 voporizes, the mercury will be forced down in the manometer and may be
completely displaced from the manometer tube, thus preventing an explosion.

Prior to starting this experiment, read the experiment very carefully, and if any operation is
not clear, ask for help. Although a vacuum line can be dangerous if improperly used. No
difficulties should be encountered if the instructions are followed carefully. Take your time!

In the first portion of the experiment you will introduce BF 3 into the line, transfer it from
trap, measure its vapor pressure at 111,6 oC determine its molecular weigth, and finally react it
with (CH3)3N. The product. (CH3)3N : BF3, will then be sublimed under vacuum and
characterized by its melting point and infrared spectrum.

If the vacuum line is already assembled, turn (use both hands!) all of the stopcocks to
determine whether they open and close easily. Regrease with Kel-F vacuum grease any that do
not. If the vacuum line is not complete, clamp the necessary equipment on the supporting rack in
the order shown in figure 19-4. Place the clamps near the stopcocks where stress will be greatest
during use. Make certain that the clamps offer firm support of the glassware but do not introduce
severe strains where breakage might occur. Be sure to clamp the ball and socket joints (Figure
19-2). On joint 1 (J1), clamp the 200ml bulb to be used in the molecular weight determination.
Close the inlet stopcock and stopcocks S4 and S5; open all of the others. After greasing the male
joint of the cold trap, twist on the trap to give a tight seal. Start the pump and evacuate. Turn all
of the stopcocks so as to evacuate the stopcock bulbs. When the line is pumped down (listen to
the pump and look at the manometers, which should read atmospheric preassure, 740 to
750mmHg), place a Dewar flask of liquid N2 (-196oC) around the cold trap. To minimize
evaporation, cover the open part of the Dewar with a cloth towel. Do not allow the level of liquid
N2 to rise above the bottom of the standard taper joint of the trap.

The order of the precending operations is important, for if the trap is cooled before
evacuating the line, liquid O2 (b.p.,-183oC) will condense in the cold trap. This will result in a
poor vacuum, since liquid O2 has a appreciable vapor pressure at -196oC. Also, an explosive
mixture might result if organic vapors were later condensed into the cold trap during the
experiment.

At this point the inlet stopcock and S4 and S5 should be closed,while all other stopcocks
are open. Close stopcocks S3. With Tygon tubing, connect Trap 1 to the BF 3 compressed gas
lecture bottle cylinder. With a wrench, open the main valve on the BF 3 lecture bottle cylinder;
make certain that the needle valve on the cylinder is closed. Open the intlet stopcock slowly to
evacuate the Tygon tubing. Close S2, thus separating the manifold and pump from the traps.

Next, place a Dewar flask containing liquid N2 around Trap 1. Cover just the bottom
portion of the trap with liquid N2; if the arms of the trap are cooled, the solid will condense in
them, reducing the capacity of the trap. You will now be able to monitor the BF 3 pressure in Trap
1 by observing the mercury manometer on the left. Open the needle valve on the lecture bottle
slowly, nothing the pressure. Deposit 2 to 3 g (estimate) of BF 3 (density of solid is 1.9g/ml) in
Trap 1. Do not allow the pressure to rise above 200 torr. When sufficient BF 3 has been added,
close the needle valve on the lecture bottle, close the inlet stopcock, and finally close the main
valve on the lecture bottle.Any leaks in the system will be apparent, as BF3 fumes in air.

Prepare a liquid N2-CS2 slush bath in a small Dewar flask. Fill the Dewar to within 8 cm
of the stop with CS2. While strring vigorously, add liquid N2 until the slush has the consistency of
a thick malted milk. (Do not allow a crust to form on top or the Dewar could break.) the
temperature of the slush bath is the melting point of CS2, - 111.6oC.

Remove the liquid N2 Dewar from Trap 1 and put it around Trap 2. Allow the BF 3 to
liquefy. Control the rate of warming with the CS 2 slush, but do not allow the pressure to exceed
280 to 290 torr. When a pressure of approximately 280 torr is observed, place the CS 2 slush bath
around Trap 1. Distill all of the BF3 into Trap 2. When the transfer is complete as indicated by the
pressure, close S1.

Open S2,S3, and the stopcock on the molecular weight bulb, and equalize the pressure in
the two Hg columns. Close S2 and S3. Allow Trap 2 to warm to -111.6 oC and place the CS2 slush
bath around it. Measure the vapor pressure of BF 3 at this temperature. It should be roughly 300
torr.

Open S3, allowing the preweighed and evacuated molecular weight bulb to be filled with
BF3 at the observed pressure. Close the stopcock on the bulb and condense the residual BF 3 back
into Trap 2 with the liquid N2 Dewar. Close S3 and open S4, allowing the removal of the bulb.
(not that the (CH3)3N lecture bottle in figure 19-4 has not yet been attached.) after wiping off the
stopcock grease, weigh the bulb; from its volume (fill with water and weigh; determine the
volume using the density of water), temperature, and pressure, calculate the molecular weight of
the gas.

Attach Trap 3 to joint 1 (J1) and join the (CH3)3N compressed gas lecture bottle cylinder
to S4 with Tygon tubing. Evacuate the system by opening S2, S3, and S4. Then close S2 and S3.
Replace the liquid N2 Dewar on trap 2 with the CS 2 slush. Place the liquid N2 Dewar around Trap
3. Open the main valve on the (CH 3)3N lecture bottle, and then with the needle valve, allow
about 5g of (CH3)3N to slowly condense into trap 3. Close the needle valve, S4, and the main
valve on the cylinder. Then slowly condense all of the BF 3 in trap 2 into trap 3 by opening S3.
The heat generated by this highly exothermic reaction will significantly increase the pressure in
the system, and if uncontrolled will force the mercury out of the monometer. The BF 3 should
therefore be added slowly and in about three portios. After adding each portion, remove the N2
Dewar and Allow the mixture to liquefy and react. When the BF3 is completely transferred,
replace the liquid N2 Dewar with the CS2 slush and allow Trap 3 to warm to -111.6 oC over a 15
minute period. Any excess gases by allowing it to remain in the dynamic vacuum for 30 minutes
at room temperature. Close S3, remove the (CH 3)3N : BF3, in trap 3 is freed of excess gases by
allowing it to remain in the dynamic vacuum for 30 minutes at room temperature. Close S3,
remove the (CH3)3N lecture bottle, open S4, and remove trap 3. The product is stable in air.

Shut down the vacuum line as folloes : 1. Remove the liquid N 2 Dewar from the cold trap;
2. Turn off the vacuum pump; 3. Open S5 and 4. Remove the cold trap and place it in the hood,
to allow volatile substances to evaporate.

Sublime (CH3)3N : BF3 under vacuum at 110oC (Figure 11-3). Determine the melting point
of the sublimed product in a sealed ( at both ends) capillary tube. Record the infrared spectrum of
the adduct in CHCl3 or CH2Cl2 solvent (experiment 14, p 136)