5 Six Gas Laws and Solved Problems
5 Six Gas Laws and Solved Problems
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Suppose the volume is increased. This means gas molecules have farther to go and they will
affect the container walls less often collisions per unit time. This means the gas pressure will
be less because there are less molecule impacts per unit time. If the volume is decreased, the
gas molecules have a shorter distance to go, thus striking the walls more often per unit time.
This results in pressure being increased because there are more molecules’ impacts per unit
time.
Now, if the volume is changed to a new value called V2, then the pressure will spontaneously
change to P2. It will do so because the PV product must always equal k. The PV product
CANNOT just change to any old value. It MUST go to k (If the temperature and amount
remain the same.) Of course, you now want to ask, "Why does it have to stay at k?" We
believe it is best right now to ignore that question even though it is a perfectly valid one.
And we know that the second data pair equals the same constant P2 V2 = k
Example #1:
2.00 L of a gas is at 740.0 mm Hg pressure. What is its volume at standard pressure?
Example #2:
5.00 L of a gas is at 1.08 atm. What pressure is obtained when the volume is 10.0 L?
Example #3:
2.50 L of a gas was at an unknown pressure. However, at standard pressure, its volume was
measured to be 8.00 L. What was the unknown pressure?
Answer: notice the units of the pressure were not specified, so any can be used. If this were a
test question, you might want to inquire of the teacher as to a possible omission of desired
units. Let's use kPa since the other two units were used above. Once again, insert into
P1V1 = P2V2 for the solution.
You can see that Boyle's Law problems all use the same solution technique. It is just a
question of where the x is located. Two problems will arise during the gas laws unit in your
classroom:
How to match a given problem with what law it is, so you can solve it.
Watching out for questions worded in a slightly confusing manner or with unnecessary
information.
Regarding the picture of Robert Boyle, be safe to note that this is not his real hair. Wigs were
the fashion in his days.
The table below shows the values Boyle collected. The titles of each column are rather wordy
and so are given below the table. All measurements are in inches.
It was published in "A Defense of the Doctrine Touching the Spring And Weight of the
Air . . . .," published in 1662.
A B C D E
For the better understanding of this experiment, it may not be a miss to take notice of the
following particulars:
1. That the tube being so tall, that we could not conveniently make use of it in a chamber, we
were fain to use it on a pair of stairs, which yet were very lightsome, the tube being for
preservation's sake by strings so suspended, that it did scarce touch the box presently to be
mentioned.
2. The lower and crooked part of the pipe was placed in a square wooden box, of a good
largeness and depth, to prevent the loss of the quicksilver, that might fall aside in the
transfusion from the vessel into the pipe, and to receive the whole quicksilver in case the
tube should break.
3. That we were two to make the observation together, the one to take notice at the bottom,
how the quicksilver rose in the shorter cylinder, and the other to pour in at the top of the
longer; it being very hard and troublesome for one man alone to do both accurately.
4. That the quicksilver was poured in but by little and little, according to the direction of him
that observed below; it being far easier to pour in more, than to take out any, in case too
much at once had been poured in.
The following figure is from an article in the May 1992 issue of the Journal of College Science
Teaching. Pages 363-365 is an excellent article by Frank Fazio titled "Using Robert Boyle's
Original Data in the Physics and Chemistry Classrooms."
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2. Charles' Law
Discovered by Joseph Louis Guy-Lussac in 1802. He made reference in his paper to
unpublished work done by Jacques Charles about 1787 (he died in 1850). Charles had found
that oxygen, nitrogen, hydrogen, carbon dioxide, and air expand to the same extent over the
same 80 degree interval.
Charles did invent the hydrogen-filled balloon and on December 1, 1783, he ascended into the
air and became possibly the first man in history to witness a double sunset.
Guy-Lussac was no slouch in the area of ballooning. On September 16, 1804, he ascended to
an altitude of 7016 meters (just over 23,000 feet - about 4.3 miles). This remained the world
altitude record for almost 50 years when that record was broken by only a few meters.
Because of Guy-Lussac's reference to Charles' work, many people have come to call the law
by the name of Charles' Law. There are some books which call the temperature-volume
relationship by the name of Guy-Lussac's Law, and there are some which call it the Law of
Charles and Guy-Lussac. Needless to say, there are some confused people out there. Most
textbooks call it Charles' Law.
The same year a 23-year-old Guy-Lussac discovered this law, he had occasion to walk into a
linen draper's shop in Paris and there he made a wonderous discovery. He found the 17-years
old showgirl reading a chemistry textbook while waiting for customers. Needless to say, he
was intrigued by this, and made more visits to the shop. In 1808, he and Josephine were
married and over the years, five little Guy-Lussac ankle-biters were added to the scene.
This law gives the relationship between volume and temperature if pressure and amount are
held constant. If the temperature of a container is increased, the volume increases. If the
temperature of a container is decreased, the volume decreases.
Why?
Suppose the temperature is increased. This means gas molecules will move faster and they will
impact the container walls more often. This means the gas pressure inside the container will
increase (but only for an instant. Think of a short span of time.). The greater pressure on the
inside of the container walls will push them outward, thus increasing the volume. When this
happens, the gas molecules will now have farther to go, thereby lowering the number of
impacts and dropping the pressure back to its constant value.
It is important to note that this momentary increase in pressure lasts for only a very, very
small fraction of a second. You would need a very fast, accurate pressure-sensing device to
measure this momentary change.
Charles' Law is a direct mathematical relationship. This means there are two connected
values and when one goes up, the other also increases.
The new temperature-volume data pair will preserve the value of k. We do not care what the
actual value of k is, only that two different temperature-volume data pairs equal the same
value and that value is called k.
So we know this: T1 ÷ V1 = k
Notice that the right-hand equation results from cross-multiplying the first one. Some people
remember one better than the other, so both are provided.
Example # 1:
A gas is collected and found to fill 2.85 L at 25.0°C, what will be its volume at standard
temperature?
Answer:
convert 25.0°C to Kelvin and you get 298 K. Standard temperature is 273 K. We plug into our
equation like this:
Remember that you have to plug into the equation in a very specific way. The temperatures
and volumes come in connected pairs and you must put them in the proper place.
Example # 2:
4.40 L of a gas is collected at 50.0°C, what will be its volume upon cooling to 25.0°C?
First of all, 2.20 L is the wrong answer. Sometimes a student will look at the temperature
being cut in half and reason that the volume must also be cut in half. That would be true if the
temperature was in Kelvin. However, in this problem the Celsius is cut in half, not the Kelvin.
Answer:
convert 50.0°C to 323 K and 25.0°C to 298 K. Then plug into the equation and solve for x, like
this:
Example # 3:
5.00 L of a gas is collected at 100 K and then allowed to expand to 20.0 L. What must the new
temperature be in order to maintain the same pressure (as required by Charles' Law)?
Answer:
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3. Guy-Lussac's Law
Discovered by Joseph Louis Guy-Lussac in the early 1800's. It gives the relationship between
pressure and temperature when volume and amount are held constant. If the temperature of
a container is increased, the pressure increases. If the temperature of a container is decreased,
the pressure decreases.
Why?
Suppose the temperature is increased. This means gas molecules will move faster and they will
impact the container walls more often. This means the gas pressure inside the container will
increase, since the container has rigid walls (volume stays constant).
Guy -Lussac's Law is a direct mathematical relationship. This means there are two connected
values and when one goes up, the other also increases.
As with the other laws, the exact value of k is unimportant in our context. It is important to
know the PT data pairs obey a constant relationship, but it is not important for us what the
exact value of the constant is. Besides which, the value of k would shift based on what
pressure units (atm, mmHg, or kPa) you were using.
We know this: P1 ÷ T1 = k
Notice the similarities to the Charles' Law. This is because both laws are direct relationships.
Make sure to convert any Celsius temperature to Kelvin before using it in your calculation.
Example # 1:
10.0 L of a gas is found to exert 97.0 kPa at 25.0°C. What would be the required temperature
(in Celsius) to change the pressure to standard pressure?
Answer:
change 25.0°C to 298.0 K and remember that standard pressure in kPa is 101.325. Insert
values into the equation and get:
The answer is 311.3 K, but the question asks for Celsius, so you subtract 273 to get the final
answer of 38.3°C, but then you knew that. Right?
Example #2:
5.00 L of a gas is collected at 22.0°C and 745.0 mmHg. When the temperature is changed to
standard, what is the new pressure?
Answer:
convert to Kelvin and insert:
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4. Avogadro's Law
Discovered by Amedo Avogadro, of Avogadro's Hypothesis fame, probably sometime in the
early 1800s. It gives the relationship between volume and amount when pressure and
temperature are held constant. Remember amount is measured in moles. Also, since volume is
one of the variables, that means the container holding the gas is flexible in some way and can
expand or contract. If the amount of gas in a container is increased, the volume increases. If
the amount of gas in a container is decreased, the volume decreases.
Why?
Suppose the amount is increased. This means there are more gas molecules and this will
increase the number of impacts on the container walls. This means the gas pressure inside the
container will increase (for an instant), becoming greater than the pressure on the outside of
the walls. This causes the walls to move outward. Since there is more wall space the impacts
will lessen and the pressure will return to its original value.
Let V1 and n1 be a volume-amount pair of data at the start of an experiment. If the amount is
changed to a new value called n2, then the volume will change to V2.
We know this: V1 ÷ n1 = k
Example #1:
5.00 L of a gas is known to contain 0.965 mol. If the amount of gas is increased to 1.80 mol,
what new volume will result (at an unchanged temperature and pressure)? Answer: this time
I'll use V1n2 = V2n1
Step 4: Take the square root to get the combined gas law:
P1 V1 / T1 = P2 V2 / T2
If all six gas laws are included (the three above as well as Avogadro, Diver, and "no-name"),
we would get the following:
P1 V1 / n1 T1 = P2 V2 / n2 T2
However, this more complete combined gas law is rarely, if ever, discussed. Consequently, we
will ignore it in future discussions and use only the law given in step 4 above.
Problem
The following type of combined gas law problem (where everything goes to STP) is VERY
common:
2.00 L of a gas is collected at 25.0°C and 745.0 mmHg. What is the volume at STP?
(Note: STP is a common abbreviation for "standard temperature and pressure.")
You have to recognize that five values are given in the problem and the sixth is an unknown x.
Remember to change the Celsius temperatures into Kelvin.
To solve the problems, write it as a matrix, like this:
and fill it in with data from the problem. Here is the right-hand side filled in with the STP
values:
Insert the values in their proper places in the combined gas law equation:
P1V1 / T1 = P2V2 / T2
and solve for x.
Problem
The next problem uses two gas laws in sequence. It involves using Dalton's Law of Partial
Pressures first, then use of the Combined Gas Law. The explanation will assume you
understand Dalton's Law. These two laws occurring together in a problem is VERY
COMMON.
1.85 L of a gas is collected over water at 98.0 kPa and 22.0°C., what is the volume of the dry
gas at STP?
The key phrase is "over water." Another phrase to look for is "wet gas." This means the gas
was collected by bubbling it into an inverted bottle filled with water that is sitting in a water
bath. The gas bubbles-in, and is trapped. It displaces the water that flows out into the water
bath.
The problem is that the trapped gas now has water vapor mixed in with it. This is a
consequence of the technique and cannot be avoided. However, we can use a preparatory
calculation technique based on Dalton's Law. That calculation should allow us to remove the
effect of the water vapor and treat the gas as "dry." For this example, we write Dalton's Law
like this:
We need to know the vapor pressure of water at 22.0°C and to do this we must look it up in a
reference source.
It is important to recognize the P tot is the 98.0 value. P tot is the combined pressure of the dry
gas AND the water vapor. We want the water vapor pressure OUT.
We solve the problem for P gas and get 95.3553 kPa. Notice that it is not rounded off. The only
rounding off done is at the FINAL answer, which this is not.
Placing all the values into the solution matrix yields this:
k1 = atm-L
k2 = L / K
k3 = atm / K
k4 = L / mol
k5 = atm / mol
1 / k6 = 1 / mol-K
Each unit occurs three times and the cube root yields L-atm / mol-K, the classic units for R
when used in a gas law context.
Resuming, we have:
PV / n T = R
PV = n R T
R is called the gas constant. Sometimes it is referred to as the universal gas constant. If you
wind up taking enough chemistry, you will see it showing up over and over and over.
R's value can be determined many ways. This is just one way:
We will assume we have 1.000 mol of a gas at STP. The volume of this amount of gas under
the conditions of STP is known to a high degree of precision. We will use the value of 22.414
L.
By the way, 22.414 L at STP has a name. It is called "molar volume." It is the volume of ANY
ideal gas at standard temperature and pressure.
Notice how atmospheres were used as well as the exact value for standard temperature.
Solving for R gives 0.08206 L atm / mol K, when rounded to four significant figures. This is
usually enough. Remember the value. You'll need it for problem solving.
Notice the weird unit on R: say out loud "liter atmospheres per mole Kelvin."
This is not the only value of R that can exist. It depends on which units you select.
Those who take more chemistry will meet up with 8.3145 Joules per mole Kelvin, but we will
only use the 0.08206 value in gas-related problems.
A sample of dry gas weighing 2.1025 grams is found to occupy 2.850 L at 22.0°C and 740.0
mmHg. How many moles of the gas are present?
Notice that the units for pressure MUST be in atm., so the 740.0 mm Hg must be converted
first.
However, the unrounded-off value should be used in the calculation just below.
When using the problem above, what is the molar mass of the gas?
This is a very common use of this law and the odds are very good you will see this type of
question on a test.
The key is to remember the units on molar mass: grams per mole.
We know from the problem statement that 2.1025 grams of the gas is involved and we also
know how many moles that is.
We know that from doing the calculation above and getting 0.1146 mol.
So all we have to do is divide the grams of gas by how many moles it is:
2.1025 g ÷ 0.1146 mol = 18.34 g/mol
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Dalton's Law of Partial Pressures
John Dalton discovered this law in 1801. For any pure gas (let's use helium), PV = n R T holds
true. Therefore, P is directly proportional to n if V and T remain constant. As n goes up, so
would P. Or the reverse.
Example
Suppose you were to double the moles of helium gas present. What would happen?
Answer: the gas pressure doubles.
However, suppose the new quantity of gas added was a DIFFERENT gas. Suppose that,
instead of helium, you added neon. What would happen to the pressure?
Answer: the pressure doubles, same as before.
Derivation
Dalton's Law immediately follows from this example since each gas is causing 50% of the
pressure. Summing their two pressures gives the total pressure. Written as an equation, it
looks like this:
P He + P Ne = P total
Dalton's Law of Partial Pressures: each gas in a mixture creates pressure as if the other gases
were not present. The total pressure is the sum of the pressures created by the gases in the
mixture.
P total = P 1 + P 2 + P 3 + .... + P n
The only necessity is that the two gases do not interact in some chemical fashion, such as
reacting with each other. The pressure each gas exerts in mixture is called its partial pressure.
The most common use of Dalton's Law seen is with water vapor.
We get it from a table because the water vapor pressure depends only on the temperature,
NOT how big the container is or the pressure of the other gas. Usually the textbook will have
an abbreviated table with more complete tables in reference manuals like "The Handbook of
Chemistry and Physics."
So finally, here is the example problem: 0.750 L of a gas is collected over water at 23.0°C with
a total pressure of 99.75 kPa. What is the pressure of the dry gas? Look up the vapor pressure
data here.
Work this problem one out!
Example
Another common concept that crops up in a Dalton's Law context is the mole fraction.
Suppose you had equal moles of two different gases in a mixture. Then the mole fraction for
each would be 0.50. The mole fraction for each gas is simply the moles of that gas divided by
the total moles in the mixture. Seems simple enough. How does it relate to Dalton's Law?
Answer:
The mole fraction also gives the fraction of the total pressure each gas contributes. So if the
mole fraction for a gas was 0.50, then it would contribute 50% of the total pressure. If the
mole fraction of a gas was 0.15, then its partial pressure would be 0.15 times the total
pressure. The reverse is also true. If you divided the partial pressure of a gas by the total
pressure, you would get the mole fraction for that gas. (I hope you know enough by now that
the two pressures would have to be in the same units!)
By the way, mole fractions are unit-less numbers. The mole (or pressure) units cancel out.
Graham's Law
Discovered by Thomas Graham of Scotland in the 1830s (I think!).
Consider samples of two different gases at the same Kelvin temperature. Since temperature is
proportional to the kinetic energy of the gas molecules, the kinetic energy of the two gas
samples is also the same.
KE1 = KE2
m1 v1 2 = m2 v2 2
Note that the value of one-half cancels. The equation above can be rearranged algebraically
into the following:
(m1 / m2)1/2 = v2 / v1
Abbreviations Conversions
Problems
136. If equal amounts of helium and argon are placed in a porous container and allowed to
escape, which gas will escape faster and how much faster?
137. What is the molecular weight of a gas which diffuses 1/50 as fast as hydrogen?
138. Two porous containers are filled with hydrogen and neon respectively. Under identical
conditions, 2/3 of the hydrogen escapes in 6 hours. How long will it take for half the neon to
escape?
139. If the density of hydrogen is 0.090 g/L and its rate of diffusion is 6 times that of chlorine,
what is the density of chlorine?
140. How much faster does hydrogen escape through a porous container than sulfur dioxide?