14.

7 Avogadro's Law

[Figure 1]

How much air do you put into a tire?

A flat tire is not very useful. It does not cushion the rim of the wheel and creates a very uncomfortable
ride. When air is added to the tire, the pressure increases as more molecules of gas are forced into the
rigid tire. How much air should be put into a tire depends on the pressure rating for that tire. Too little
pressure and the tire will not hold its shape. Too much pressure and the tire could burst.

Avogadro’s Law

You have learned about Avogadro’s hypothesis: equal volumes of any gas at the same temperature and
pressure contain the same number of molecules. It follows that the volume of a gas is directly
proportional to the number of moles of gas present in the sample. Avogadro’s law states that the
volume of a gas is directly proportional to the number of moles of gas when the temperature and
pressure are held constant. The mathematical expression of Avogadro’s law is

where n is the number of moles of gas and k is a constant. Avogadro’s law is in evidence whenever you
blow up a balloon. The volume of the balloon increases as you add moles of gas to the balloon by
blowing it up. If the container holding the gas is rigid rather than flexible, pressure can be substituted for
volume in Avogadro’s law. Adding gas to a rigid container makes the pressure increase.

Sample Problem: Avogadro’s Law

A balloon has been filled to a volume of 1.90 L with 0.0920 mol of helium gas. If 0.0210 mol of additional
helium is added to the balloon while the temperature and pressure are held constant, what is the new
volume of the balloon?
Step 1: List the known quantities and plan the problem.
Known
Note that the final number of moles has to be calculated by adding the original number of moles
to the moles of added helium. Use Avogadro’s law to solve for the final volume.

Since a relatively small amount of additional helium was added to the balloon, its volume increases
slightly.

Example #2: A cylinder with a movable piston contains 2.00 g of helium, He, at room temperature. More
helium was added to the cylinder and the volume was adjusted so that the gas pressure remained the
same. How many grams of helium were added to the cylinder if the volume was changed from 2.00 L to
2.70 L? (The temperature was held constant.)

Solution:

1) Convert grams of He to moles:

2.00 g / 4.00 g/mol = 0.500 mol

2) Use Avogadro's Law:

V1 / n1 = V2 / n2 = 2.00 L / 0.500 mol = 2.70 L / x

x = 0.675 mol

3) Compute grams of He added:

0.675 mol − 0.500 mol = 0.175 mol

(0.175 mol) (4.00 g/mol) = 0.7 grams of He added

Example #3: A container with a volume of 25.47 L holds 1.050 mol of oxygen gas (O2) whose molar mass
is 31.9988 g/mol. What is the volume if 7.210 g of oxygen gas is removed from the container, assuming
the pressure and temperature remain constant?

Solution #1:

1) Initial mass of O2: (1.050 mol) (31.9988 g/mol) = 33.59874 g

2) Final mass of O2: 33.59874 − 7.210 = 26.38874 g

3) Final moles of O2: 26.38874 g / 31.9988 g/mol = 0.824679 mol

4) Use Avogadro's Law:

V1 / n1 = V2 / n2 = 25.47 L / 1.050 mol = V2 / 0.824679 mol

V2 = 20.00 L

Summary

 Calculations are shown for relationships between volume and number of moles of gas.

Review:

1. What is held constant in the Avogadro’s Law relationship?

2. What happens if you add gas to a rigid container?
3. Why does a balloon expand when you add air to it?
4. If 3.25 mol of argon gas occupies a volume of 100. L at a particular temperature and
pressure, what volume does 14.15 mol of argon occupy under the same conditions?
5. 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)?
Ideal Gas Law

[Figure 1]

What chemical reactions require ammonia?

There are a number of chemical reactions that require ammonia. In order to carry out the reaction
efficiently, we need to know how much ammonia we have for stoichiometric purposes. Using gas laws,
we can determine the number of moles present in the tank if we know the volume, temperature,
and pressure of the system.

Ideal Gas Law

The combined gas law shows that the pressure of a gas is inversely proportional to volume and directly
proportional to temperature. Avogadro’s law shows that volume or pressure is directly proportional to
the number of moles of gas. Putting these together leaves us with the following equation:
The variable R in the equation is called the ideal gas constant.

Evaluating the Ideal Gas Constant

The value of R, the ideal gas constant, depends on the units chosen for pressure, temperature, and
volume in the ideal gas equation. It is necessary to use Kelvin for the temperature and it is conventional
to use the SI unit of liters for the volume. However, pressure is commonly measured in one of three
units: kPa, atm, or mmHg. Therefore, R can have three different values.
We will demonstrate how R is calculated when the pressure is measured in kPa. Recall that the volume
of 1.00 mol of any gas at STP is measured to be 22.414 L. We can substitute 101.325 kPa for pressure,
22.414 L for volume, and 273.15 K for temperature into the ideal gas equation and solve for R.

Sample Problem # 1: Ideal Gas Law

What volume is occupied by 3.760 g of oxygen gas at a pressure of 88.4 kPa and a temperature of 19°C?
Assume the oxygen is ideal.

Step 1: List the known quantities and plan the problem.

Known
Step 3: Think about your result
.
The number of moles of oxygen is far less than one mole, so the volume should be fairly small compared
to molar volume (22.4 L/mol) since the pressure and temperature are reasonably close to standard. The
result has three significant figures because of the values for T and P. Since a joule (J) = kPa • L, the units
cancel correctly, leaving a volume in liters.

Sample problem #2: Determine the volume of occupied by 2.34 grams of carbon dioxide gas at STP.

Solution:

1) Rearrange PV = nRT to this:V = nRT / P

2) Substitute:

V = [(2.34 g / 44.0 g mol¯1) (0.08206 L atm mol¯1 K¯1) (273.0 K)] / 1.00 atm

V = 1.19 L (to three significant figures)

Sample problem #3:A sample of argon gas at STP occupies 56.2 liters. Determine the number of moles of
argon and the mass of argon in the sample.

Solution:

1) Rearrange PV = nRT to this: n = PV / RT

2) Substitute: n = [(1.00 atm) (56.2 L) ] / [ (0.08206 L atm mol¯1 K¯1) (273.0 K)]

n = 2.50866 mol (I'll keep a few guard digits)

3) Multiply the moles by the atomic weight of Ar to get the grams:

2.50866 mol times 39.948 g/mol = 100. g (to three sig figs)

Problem #4: At what temperature will 0.654 moles of neon gas occupy 12.30 liters at 1.95 atmospheres?

Solution:

1) Rearrange PV = nRT to this: T = PV / nR

2) Substitute:

T = [(1.95 atm) (12.30 L)] / [(0.654 mol) (0.08206 L atm mol¯1 K¯1)]

T = 447 K

Problem #5: A 40.0 g gas sample occupies 11.2 L at STP. Find the molecular weight of this gas.

Solution:

11.2 L at STP is one-half molar volume, so there is 0.500 mol of gas present. Therefore, the molecular
weight is 80.0 g mol¯1

Problem #6: A 12.0 g sample of gas occupies 19.2 L at STP. What is the molecular weight of this gas?

Solution:This problem, as well as the two just above can be solved with PV = nRT. You would solve for n,
the number of moles. Then you would divide the grams given by the mole calculated.

1) Use PV = nRT:(1.00 atm) (19.2 L) = (n) (0.08206) (273 K)

n = 0.8570518 mol (I'll keep a few guard digits)

2) Determine the molecular weight:12.0 g / 0.8570518 mol = 14.0 g/mol

3) Since it is at STP, we can also use molar volume:

(19.2 L / 12.0 g) = (22.414 L / x ) = 19.2x = 268.968

x = 14.0 g/mol

Warning: you can only use molar volume when you are at STP.
Problem #7: 96.0 g. of a gas occupies 48.0 L at 700.0 mm Hg and 20.0 °C. What is its molecular weight?

Solution:

1) Solve for the moles using PV = nRT: n = PV / RT

n = [(700.0 mmHg / 760.0 mmHg atm¯1) (48.0 L)] / [(0.08206 L atm mol¯1 K¯1) (293.0 K)]

n = 1.8388 mol

2) Divide the grams given (96.0) by the moles just calculated above:

96.0 g / 1.8388 mol = 52.2 g/mol

Summary

 The ideal gas constant is calculated.

 An example of calculations using the ideal gas law is shown.

Review

1. Which value of R will you use if the pressure is given in atm?

2. You are doing a calculation where the pressure is given in mm Hg. You select 8.314 J/K • mol as your
value for R. Will you get a correct answer?

3. How would you check that you have chosen the correct value of R for your problem?

4. How many moles of gas does it take to occupy 120 liters at a pressure of 2.3 atmospheres and a
temperature of 340 K?

5) If I have a 50 liter container that holds 45 moles of gas at a temperature of 2000 C, what is the
pressure inside the container?

6) How many moles of gas are in a 30 liter scuba canister if the temperature of the canister is 300 K and
the pressure is 200 atmospheres